Organoaminosilanes and methods for making same

ABSTRACT

Organoaminosilanes, such as without limitation di-iso-propylaminosilane (DIPAS), are precursors for the deposition of silicon containing films such as silicon-oxide and silicon-nitride films. Described herein are methods to make organoaminosilane compounds, or other compounds such as organoaminodisilanes and organoaminocarbosilanes, via the catalytic hydrosilylation of an imine by a silicon source comprising a hydridosilane.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the priority benefit of U.S. ProvisionalApplication Ser. No. 61/946,164 filed Feb. 28, 2014 which isincorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION

Described herein are methods for making organoaminosilane compounds thatmay be useful, for example, as chemical precursor for depositing asilicon-containing film. Also described herein are compounds, morespecifically organoamines, organoaminosilane, organoaminodisilane,and/or organoaminocarbosilane compounds, that are suitable for use in avariety of industrial applications.

Organoaminosilanes containing the —SiH₃ or —SiH₂— moieties are desirableprecursors for the deposition of silicon-containing films such as,without limitation, silicon oxide and silicon nitride films or dopedversions thereof. For example, volatile compounds such as withoutlimitation organoaminosilanes, organoaminodisilanes, and/ororganoaminocarbosilanes are important precursors used for the depositionof silicon-containing films in the manufacture of semiconductor devices.One particular embodiment of an organoaminosilane compound isdi-iso-propylaminosilane (DIPAS), which has previously been shown toexhibit desirable physical properties for the controlled deposition ofsuch films. Although DIPAS can be prepared by the direct reaction ofdi-iso-propylamine (DIPA) or lithium-di-iso-propylamide withmonochlorosilane (MCS) or monochlorodisilane (MCDS), MCS or MCDS is notan abundant commodity chemical and is therefore subject to limitedavailability and price instability. Furthermore, synthesis oforganoaminosilanes using MCS may produce stoichiometric amounts of aminehydrochloride salts that can be highly absorbent thereby complicatingrecovery of organoaminosilane products.

The prior art describes some methods for the production oforganoaminosilane compounds. Japanese Patent JP49-1106732 describes amethod for preparing silylamines by the reaction of an imine and ahydridosilane in the presence of a rhodium (Rh) complex. Exemplarysilylamines that were prepared include: PhCH₂N(Me)SiEt₃,PhCH₂N(Me)SiHPh₂, PhCH₂N(Ph)SiEt₃, and PhMeCHN(Ph)SiHEt₂ wherein “Ph”means phenyl, “Me” means methyl, and “Et” means ethyl.

U.S. Pat. No. 6,072,085 describes a method for preparing a secondaryamine from a reaction mixture comprising an imine, a nucleophilicactivator, a silane, and a metal catalyst. The catalyst acts to catalyzethe reduction of the imine by a hydrosilylation reaction.

U.S. Pat. No. 6,963,003, which is owned by the assignee of the presentapplication, provides a method for preparing an organoaminosilanecompound comprising reacting a stoichiometric excess of at least oneamine selected from the group consisting of secondary amines having theformula R¹R²NH, primary amines having the formula R²NH₂ or combinationsthereof with at least one chlorosilane having the formula R³_(n)SiCl_(4-n) under anhydrous conditions sufficient such that a liquidcomprising the aminosilane product and an amine hydrochloride salt isproduced wherein R¹ and R² can each independently be a linear, cyclic orbranched alkyl group having 1 to 20 carbon atoms; R³ can be a hydrogenatom, an amine group, or a linear, cyclic or branched alkyl group having1 to 20 carbon atoms; and n is a number ranging from 1 to 3.

U.S. Pat. No. 7,875,556, which is owned by the assignee of the presentapplication, describes a method for making an organoaminosilane byreacting an acid with an arylsilane in the presence of a solvent, addinga secondary amine and tertiary amine, and removing the reactionbyproduct using phase separation and the solvent using distillation.

U.S. Publ. No. 2012/0277457, which is owned by the assignee of thepresent application, describes a method for making an organoaminosilanecompound having the following formula:

H₃SiNR¹R²

wherein R¹ and R² are each independently selected from C₁-C₁₀ linear,branched or cyclic, saturated or unsaturated, aromatic, heterocyclic,substituted or unsubstituted alkyl groups wherein R¹ and R² are linkedto form a cyclic group or wherein R¹ and R² are not linked to form acyclic group comprising the steps of: reacting a halosilane having theformula H_(n)SiX_(4-n) wherein n is 0, 1, or 2 and X is Cl, Br, or amixture of Cl and Br, with an amine to provide a slurry comprising ahaloaminosilane compound X_(4-n)H_(n-1)SiNR¹R² wherein n is a numberselected from 1, 2 and 3; and X is a halogen selected from Cl, Br, or amixture of Cl and Br; and introducing into the slurry a reducing agentwherein at least a portion of the reducing agent reacts with thehaloaminosilane compound and provides an end product mixture comprisingthe aminosilane compound.

Korean Patent No. 10-1040325 provides a method for preparing analkylaminosilane which involves reacting a secondary amine andtrichloroalkylsilane in an anhydrous atmosphere and in the presence of asolvent to form an alkyl aminochlorosilane intermediate and a metalhydride LiAlH₄ is added to the alkyl aminochlorosilane intermediate as areducing agent to form the alkylaminosilane. The alkylaminosilane isthen subjected to a distillation process to separate and purify thealkylaminosilane.

Reference article entitled “Homogeneous Catalytic Hydrosilylation ofPyridines”, L. Hao et al., Angew. Chem., Int. Ed., Vol. 37, 1998, pp.3126-29 describes the hydrosilylation of pyridines, e.g. RC₅H₄N (R=H,3-Me, 4-Me, 3-CO₂Et), by PhSiH₂Me, Ph₂SiH₂ and PhSiH₃ in the presence ofa titanocene complex catalyst such as a [Cp₂TiMe₂], which provided highyields of 1-silylated tetrahydropyridine derivatives and theintermediate silyltitanocene adduct, Cp₂Ti(SiHMePh)(C₅H₅N) (I).

Reference article entitled “Stoichiometric Hydrosilylation of Nitrilesand Catalytic Hydrosilylation of Imines and Ketones Using a μ-SilaneDiruthenium Complex”, H. Hashimoto et al., Organometallics, Vol. 22,2003, pp. 2199-2201 describes a method to synthesize p-iminosilylcomplexes Ru₂(CO)₄(μ-dppm)(μ-SiToI₂)(μ-RCH:NSiToI₂) (R=Me, Ph, t-Bu,CH:CH₂) in high yields during the stoichiometric reactions of adiruthenium complex having Ru—H—Si interactions,{Ru(CO)₂(SiToI₂H)}₂(μ-dppm)(μ-η²:η²-H₂SiToI₂), with nitriles RCN.

Reference article entitled “Titanocene-Catalyzed Hydrosilylation ofImines: Experimental and Computational Investigations of theCatalytically Active Species”, H. Gruber-Woelfler et al.,Organometallics, Vol. 28, 2009, pp. 2546-2553 described the asymmetricalcatalytic hydrosilylation of imines using(R,R)-ethylene-1,2-bis(η⁵-4,5,6,7-tetrahydro-1-indenyl)titanium(R)-1,1′-binaphth-2-olate (1) and(S,S)-ethylene-1,2-bis(η⁵-4,5,6,7-tetrahydro-1-indenyl)titaniumdichloride (2) as catalyst precursors. After activation with RLi(R=alkyl, aryl) and a silane, these complexes are known catalysts forhydrosilylation reactions.

Reference article “Iridium-Catalyzed Reduction of Secondary Amides toSecondary Amines and Imines by Diethylsilane”, C. Cheng et al., J. Am.Chem. Soc., Vol. 134, 2012, pp. 110304-7, describes the catalyticreduction of secondary amides to imines and secondary amines by usingiridium catalysts such as [Ir(COE)₂Cl]₂ with diethylsilane as reductant.

The prior art synthesis reactions described above suffer from variousdeficiencies. For example, in the synthesis routes that do not use acatalyst, the synthesis of organoaminosilane require multiple stepsusing, for example, (a) arylsilane, triflic acid, secondary amine, andtertiary amine, (b) silylhalogen, excess secondary amine, and metalhydride, or (c) silylhalogen, alkali metal amide, and metal hydride.Each of these synthesis routes requires significant cooling to managehighly exothermic reactions and produce significant amounts of saltbyproducts that must be subsequently removed by filtration process.

Alternatively, the synthesis reactions described above that do involvecatalytic hydrosilylation of imines, are generally used for thesynthesis of secondary amines or, alternatively, for highlightingfundamentally unique catalysts. As such, the aforementioned referencesdo not describe a method for the synthesis, isolation, and purificationof organoaminosilanes to be used, for example, as precursors for thedeposition of silicon-containing films. It should be noted further thatthere are no description in the above references wherein,silicon-containing sources such as silane (SiH₄), disilane (Si₂H₆), ormethylsilane (MeSiH₃) gas are used as the Si—H starting material orsilicon source material for the catalytic hydrosilylation of imines toform organoaminosilane or organoaminodisilane compounds, such as, forexample, di-iso-propylaminosilane (DIPAS), di-iso-propylaminodisilane(DIPADS), and di-iso-propylaminomethylsilane. Furthermore, there is noprior art that teaches the use of complexes of alkaline earth metalssuch as Ca, Sr, Ba, which are more abundant and less expensive than manytransition metals, as catalysts for the hydrosilylation of imines,whether it be for the synthesis of organoaminosilanes,organoaminodisilanes, and organoaminocarbosilanes or the synthesis oforganoamines.

Accordingly there is a need to provide a method of making compounds suchas, without limitation, organoamines, organoaminosilanes (e.g., DIPAS),organoaminodisilanes (e.g., DIPADS), and organoaminocarbosilanes, usingcommercially available reagents in relatively high yields via thecatalytic hydrosilylation of imines. There is also a need to provide amethod of making organoaminosilanes, such as without limitation, DIPAS,by a means that eliminates or facilitates the separation of the productfrom reaction mixture. There is a need to provide methods of makingorganoaminosilanes and/or organoamines that reduces the overallproduction costs by reducing the costs of reagents used and/or reducingagents. There is a need to provide a method of making organoaminosilanesand/or organoamines that eliminates hazards associated with highlyexothermic reactions such as those involving triflic acid, metal amide,and metal hydride reagents. There is a need to provide a method ofmaking organoaminosilanes and/or organoamines that avoids usinghalosilane starting materials, such that there are reduced halideimpurities in the purified product in order to avoid potential halidescontamination if the compound is used as a precursor for depositingsilicon-containing films. There is also a need for synthesis ofcompounds such as, without limitation, organoamines, organoaminosilanes,organoaminodisilanes, or organoaminocarbosilanes via hydrosilylation ofimines using cheaper, more earth abundant metal catalysts compared tothe currently widely used precious metal (Ru, Rh, Ir, Pd, and Pt)catalysts.

BRIEF SUMMARY OF THE INVENTION

Described herein is a method for making compounds, more specificallyorganoaminosilanes, organoaminodisilanes, organoaminocarbosilanes and/ororganoamines, which provides one or more of the following advantagesover prior art methods to make such compounds: (a) avoids the use ofchlorosilane reagents which could lead to chlorine impurities in the endproduct thereby eliminating chloride contamination when the end productis being used as precursors to deposit a silicon containing film; (b)avoids the need for additional filtration steps to removeamine-hydrochloride or alkali metal salt byproducts which are common inprior art methods, and/or (c) avoids the use of pyrophoric alkyllithium,metal hydride reagents, or extremely corrosive reagents such as triflicacid. In this regard, the methods described herein improve upon theprior art methods for making compounds such as organoaminosilanes,organoaminodisilanes, organoaminocarbosilanes, and organoamines in oneor more of the following ways: provides increased product purity,improves the yield of end product, and/or avoids potential environmentalhealth and safety issues. The term “organoaminosilane” as used hereinmeans a compound that includes at least one N atom, at least onecarbon-containing group, and at least one Si atom and includes, withoutlimitation, organoaminosilanes, organoaminodisilanes, andorganoaminocarbosilanes.

In one aspect, described herein is a method for preparing a compoundselected from the group consisting of an organoaminosilane, anorganoaminodisilane, and an organoaminocarbosilane comprising the stepsof: reacting an imine having a formula R—N═CR′R″ wherein R, R′ and R″are each independently selected from hydrogen, a C₁₋₁₀ linear alkylgroup, a C₃₋₁₀ branched alkyl group, a C₃₋₁₀ cyclic alkyl group, a C₂₋₁₀alkenyl group, a C₄₋₁₀ aromatic group, a C₄₋₁₀ heterocyclic group, aC₁₋₁₀ linear organoamino group, a C₂₋₁₀ branched organoamino group, asilyl group, a C₁₋₁₀ linear carbosilyl group, and a C₂₋₁₀ branchedcarbosilyl group and wherein at least one of R′ and R″ or R and R′ ornone of R′ and R″ or R and R′ are be linked to form a substituted or anunsubstituted cyclic ring and a silicon source comprising ahydridosilane in the presence of a catalyst under conditions sufficientfor the silicon source and imine to react and provide the compound. Incertain embodiments of the imine having formula R—N═CR′R″, at least oneof R′ and R″, R and R′, or both R′ and R″ and R and R′ in the formulaare linked to form the substituted or unsubstituted cyclic ring. Inalternative embodiments of the imine having formula R—N═CR′R″, neitherR′ and R″ nor R and R′ in the formula are linked to form the substitutedor unsubstituted cyclic ring. In one particular embodiment of the methoddescribed herein, the reacting step is conducted in the presence of asolvent. In an alternative embodiment of the method described herein,the reacting step is conducted in the absence of a solvent.

In another aspect, there is provided a method for preparing anorganoamine having a formula HN(R)(CHR′R″) wherein R, R′ and R″ are eachindependently selected from hydrogen, a C₁₋₁₀ linear alkyl group, aC₃₋₁₀ branched alkyl group, a C₃₋₁₀ cyclic alkyl group, a C₂₋₁₀ alkenylgroup, a C₄₋₁₀ aromatic group, a C₄₋₁₀ heterocyclic group, a C₁₋₁₀linear organoamino group, a C₂₋₁₀ branched organoamino group, a C₁₋₁₀linear carbosilyl group, and a C₂₋₁₀ branched carbosilyl group whereinat least one of R′ and R″ or R and R′, or none of R′ and R″ or R and R′are linked to form a substituted or an unsubstituted cyclic ringcomprising the steps of: forming a compound selected from anorganoaminosilane, an organoaminodisilane, and an organoaminocarbosilaneby reacting an imine having a formula R—N═CR′R″ wherein R, R′ and R″ areeach independently selected from hydrogen, a C₁₋₁₀ linear alkyl group, aC₃₋₁₀ branched alkyl or C₃₋₁₀ cyclic alkyl, C₂₋₁₀ alkenyl, C₄₋₁₀aromatic, C₄₋₁₀ heterocyclic, C₁₋₁₀ linear or C₂₋₁₀ branched organoaminogroups, a silyl group, or C₁₋₁₀ linear carbosilyl or C₂₋₁₀ branchedcarbosilyl groups wherein at least one of R′ and R″, R and R′, or noneof R′ and R″ and R and R′ are linked to form a substituted orunsubstituted cyclic ring and a silicon source comprising ahydridosilane in the presence of an alkaline earth metal catalyst underreaction conditions sufficient for the imine and silicon source to reactand provide the compound; reacting the compound with a proton sourceunder conditions sufficient to provide the organoamine. In certainembodiments, the proton source is selected from the group consisting ofwater, alcohol, or Brønsted acid.

In a further aspect, there is provided organoaminocarbosilane compoundrepresented by the following structures:

wherein R, R′ and R″ are each independently selected from hydrogen, aC₁₋₁₀ linear alkyl group, a C₃₋₁₀ branched alkyl group, a C₃₋₁₀ cyclicalkyl group, a C₂₋₁₀ alkenyl group, a C₄₋₁₀ aromatic group, a C₄₋₁₀heterocyclic group, a C₁₋₁₀ linear organoamino group, a C₂₋₁₀ branchedorganoamino groups, a silyl group, a C₁₋₁₀ linear carbosilyl group, or aC₂₋₁₀ branched carbosilyl groups and wherein at least one of R′ and R″,or R and R′, or none of R′ and R″ or R and R′ are be linked to form asubstituted or unsubstituted cyclic ring.

DETAILED DESCRIPTION OF THE INVENTION

Methods for preparing compounds such as organoaminosilanes,organoaminodisilanes, organoaminocarbosilanes, and organoamines aredescribed herein using an imine having a formula R—N═CR′R″ wherein R, R′and R″ are each independently selected from hydrogen, a C₁₋₁₀ linearalkyl group, a C₃₋₁₀ branched alkyl group, a C₃₋₁₀ cyclic alkyl group, aC₂₋₁₀ alkenyl group, a C₄₋₁₀ aromatic group, a C₄₋₁₀ heterocyclic group,a C₁₋₁₀ linear organoamino group, a C₂₋₁₀ branched organoamino group, asilyl group, a C₁₋₁₀ linear carbosilyl group, and a C₂₋₁₀ branchedcarbosilyl group and wherein R′ and R″ or R and R′ can be linked to forma substituted or an unsubstituted cyclic ring. In certain embodiments ofthe imine having formula R—N═CR′R″, R′ and R″ or R and R′ in the formulaare linked to form the substituted or unsubstituted cyclic ring. Inthese embodiments, the imine can be synthesized by condensing a primaryamine having the formula RNH₂, with a ketone or aldehyde having theformula R′R″C═O. In alternative embodiments of the imine having formulaR—N═CR′R″, R′ and R″ or R and R′ in the formula are not linked to formthe substituted or unsubstituted cyclic ring.

In the formulas above and throughout the description, the term “alkyl”denotes a linear or branched functional group having from 1 to 10 orfrom 3 to 10 carbon atoms, respectively. Exemplary linear alkyl groupsinclude, but are not limited to, methyl, ethyl, n-propyl, n-butyl,n-pentyl, and hexyl. Exemplary branched alkyl groups include, but arenot limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, iso-pentyl,tert-pentyl, isohexyl, and neohexyl. In certain embodiments, the alkylgroup may have one or more functional groups such as, but not limitedto, an alkoxy group, a dialkylamino group, an carbosilyl group, orcombinations thereof, attached thereto. In other embodiments, the alkylgroup does not have one or more functional groups attached thereto.

In the formulas above and throughout the description, the term “cyclicalkyl” denotes a cyclic functional group having from 3 to 10 or from 4to 10 carbon atoms. Exemplary cyclic alkyl groups include, but are notlimited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

In the formulas above and throughout the description, the term “aryl”denotes an aromatic cyclic functional group having from 5 to 10 carbonatoms. Exemplary aryl groups include, but are not limited to, phenyl,benzyl, chlorobenzyl, tolyl, and o-xylyl. In some embodiments, thearomatic cyclic group can have other elements such as oxygen, ornitrogen. Exemplary such groups include, but not limited to, pyrollyl,furanyl, pyridinyl, pyridazinyl.

In the formulas above and throughout the description, the term “alkenylgroup” denotes a group which has one or more carbon-carbon double bondsand has from 2 to 10 or from 2 to 6 carbon atoms. Exemplary alkenylgroups include, but are not limited to, vinyl or allyl groups.

In the formulas above and throughout the description, the term “alkynylgroup” denotes a group which has one or more carbon-carbon triple bondsand has from 2 to 10 or from 2 to 6 carbon atoms.

In the formulas above and throughout the description, the term“carbosilane” denotes an organosilane comprising carbon, hydrogen, andsilicon having from 1 to 10 carbon atoms and from 1 to 10 silicon atoms,and which contains at least one Si—C bond. Examples of carbosilanesinclude, without limitation, methylsilane, ethylsilane, diethylsilane,dimethylsilane, triethylsilane, 1,2-dimethyldisilane, 1,4-disilabutane,2-methyl-1,3-disilapropane, 1,3-disilapropane, 1-silacyclopentane,1-methyl-1-silacyclopentane, 1-silacyclobutane, 1,3-disilacyclobutane,and phenylsilane.

In the formulas above and throughout the description, the term“carbosilyl” denotes an organosilyl group comprising carbon, hydrogen,and silicon having from 1 to 10 carbon atoms and from 1 to 10 siliconatoms, and which contains at least one Si—C bond. Examples of carbosilylgroups include, without limitation, methylsilyl (—SiMeH₂), ethylsilyl(—SiEtH₂), diethylsilyl (—SiEt₂H), dimethylsilyl (—SiMe₂H),triethylsilyl (—SiEt₃), trimethylsilyl (—SiMe₃), 1,2-dimethyldisilyl(—SiMeHSiMeH₂), 1,4-disilabutyl (—SiH₂CH₂CH₂SiH₃), dimethylvinylsilyl(—SiMe₂CH═CH₂), and phenylsilyl (—SiPhH₂).

In the formulas above and throughout the description, the term “silyl”denotes the unsubstituted silyl group (—SiH₃).

In formulas above and throughout the description, the term “organoamino”denotes a dialkylamino, alkylamino, or arylalkylamino group which mayhave from 1 to 10, or from 1 to 4 carbon atoms. Exemplary organoaminogroups include, but are not limited to, dimethylamino (Me₂N—),diethylamino (Et₂N—), di-iso-propylamino (^(i)Pr₂N—),iso-propyl-sec-butylamino, N-sec-butyl-N-iso-propylamino,1-(N-ethyl-N-cyclohexylamino, N-phenyl-N-iso-propylamino,tert-butylamino (^(t)BuNH—), tert-pentylamino (^(t)AmNH—), n-propylamino(^(n)PrNH—), and iso-propylamino (^(i)PrNH—).

In certain embodiments of the formulas described herein, a substituentsuch as a cyclic ring may be substituted or have one or more atoms orgroup of atoms substituted in place of, for example, a hydrogen atom.Exemplary substituents include, but are not limited to, oxygen, sulfur,halogen atoms (e.g., F, Cl, I, or Br), nitrogen, and phosphorous. Inalternative embodiments, the substitutent is not unsubstituted.

The method described herein involves the catalytic hydrosilylation ofimines as an alternative route to the synthesis of compounds such asorganoaminosilane, organoaminodisilane, and organoaminocarbosilane whichcan be used, without limitation, as precursors in the deposition ofsilicon-containing films. For example, in one embodiment, theorganoaminosilane ^(i)Pr₂N—SiH₃ could be conveniently synthesized byreacting the imine N-iso-propyl-iso-propylidenimine with a siliconsource of silane gas SiH₄. In another embodiment, theorganoaminodisilane ^(i)Pr₂N—SiH₂SiH₃ could be obtained in a similarfashion by reacting the imine N-iso-propyl-iso-propylidenimine with asilicon source of disilane gas Si₂H₆. The method described herein can beused, for example, to prepare other organoaminosilane,organoaminodisilane, or organoaminocarbosilane compounds such as,without limitation, (organoamino)SiH₃, (organoamino)SiH₂SiH₃,(organoamino)SiH₂SiH₂(organoamino), (organoamino)SiH₂CH₂CH₂SiH₃,(organoamino)SiH₂CH₂CH₂SiH₂(organoamino), (organoamino)SiHEt₂,(organoamino)SiH(CH₂CH₂CH₂CH₂), (organoamino)SiMe(CH₂CH₂CH₂CH₂),(organoamino)SiH(CH₂CH₂CH₂), (organoamino)SiH(CH₂SiH₂CH₂),(organoamino)SiH(CH₂)₂SiH(organoamino), (organoamino)SiH₂Me, or(organoamino)SiH₂Ph. In certain embodiments, asymmetric imines could beused as a reagent in a reaction mixture comprising a silicon source inthe presence of a catalyst to provide organoaminosilanes,organoaminodisilanes, or organoaminocarbosilanes having asymmetricorganoamino groups. In this regard, these asymmetric organoaminoprecursors would otherwise have been unfeasible to synthesize usingprior art methods due to scarcity of the corresponding amine [e.g.(^(s)Bu)(^(i)Pr)NH, (^(t)Bu)(^(i)Pr)NH].

The methods described herein provide a means to synthesize desirablecompounds such as but not limited to organoaminosilanes (e.g., DIPAS),organoaminodisilanes (e.g., DIPADS), organoaminocarbosilanes, atrelatively high yields. In this regard, exemplary yields obtainable forthe compounds using the synthesis method described herein are 50 mol %or greater, 55 mol % or greater, 60 mol % or greater, 65 mol % orgreater, 70 mol % or greater, 75 mol % or greater, 80 mol % or greater,or 90 mol % or greater based on the imine usage. In synthesis processeswherein the silicon source comprises a hydridosilane reagent having atleast two Si—H groups, once one hydrosilylation has taken place at asingle silicon atom, the rate for a second, third, or fourthhydrosilylation to take place at the same silicon atom becomessignificantly and successively slower. In contrast, in synthesisprocesses involving reacting lithium-amides with Si—X_(n) (X=halide orH, n=2,3,4) compounds, or when reacting primary or secondary amines withsaid compounds, preventing over-amination is difficult. Therefore, thereis a kinetic selectivity for preparing compounds such asorganoaminosilanes in a more subtle, less harsh hydrosilylation methodsuch as the method described herein.

As previously discussed, an imine is reacted with a silicon source toform a reaction mixture comprising a compound such as withoutlimitation, an organoaminosilane (e.g., DIPAS), an organoaminodisilanes(e.g., DIPADS), and organoaminocarbosilanes. In these embodiments, thesilicon source reagent may include a hydridosilane having the formula ofR¹R²R³SiH wherein R¹, R² and R³ are each independently selected fromhydrogen, a C₁₋₁₀ linear alkyl group, a C₃₋₁₀ branched alkyl group, aC₄₋₁₀ cyclic alkyl group, a C₂₋₁₀ alkenyl group, a C₄₋₁₀ aromatic group,a C₄₋₁₀ heterocyclic group, a C₁₋₁₀ linear organoamino group, a C₂₋₁₀branched organoamino groups, a silyl group, a C₁₋₁₀ linear carbosilylgroup, and a C₂₋₁₀ branched carbosilyl group and wherein at least one ofR¹ and R², R¹ and R³, or R² and R³ or none of R¹ and R², R¹ and R³, orR² and R³ are linked to form a substituted or unsubstituted cyclic ring.

The imine reagents may include secondary aldimines, R—N═CHR′, orsecondary ketimines, R—N═CR′R″, containing linear or branched organic R,R′ and R″ functionalities and wherein R, R′ and R″ are as describedherein, though it is preferable that alkyl functionalities besufficiently large to afford stability during purification processes andstorage of the final organoaminosilane product. Exemplary iminesinclude, but are not limited to, N-iso-propyl-iso-propylidenimine,N-iso-propyl-sec-butylidenimine, N-sec-butyl-sec-butylidenimine, andN-tert-butyl-iso-propylidineimine.

The molar ratio of imine to the hydridosilane in the reaction mixtureranges from 1 to 0.5, 1 to 1, 2 to 1, 3 to 1, 5 to 1, or from 10 to 1.In embodiments wherein the hydridosilane reagent comprises only one ortwo Si—H bonds per silicon atom, the reaction may yield solely thesingly substituted amine derivative and be insensitive to higher imineratios, especially if the imine has large substituents. In embodimentswherein the hydridosilane reagent in the reaction mixture comprisesthree or more Si—H bonds per silicon atom, an excess of hydridosilane isused to avoid bis(amino)silane products. In some embodiments, thehydridosilane has only one Si—H_(x) group, wherein x is a number rangingfrom 1 to 4, such as silane, methylsilane, diethylsilane, ortrimethylsilane. In other embodiments, wherein the hydridosilane hasmore than one Si—H_(x) groups, wherein x is a number ranging from 1 to3, such as disilane, 1,4-disilabutane, or polysilanes, an excess ofhydridosilane is used if the desired organoaminodisilane ororganoaminocarbosilane product is to have only one organoamino group. Inone particular embodiment, the reaction mixture has a 1:2.2 to 1:2.3molar ratio of imine to hydridosilane to ensure the reaction proceedsquickly to completion and to prevent more than one hydrosilylationreaction per hydridosilane molecule.

The molar ratio of catalyst to imine in the reaction mixture ranges from0.1 to 1, 0.05 to 1, 0.01 to 1, 0.005 to 1, 0.001 to 1, 0.0005 to 1,0.0001 to 1, 0.00005 to 1, or 0.00001 to 1. In one particular embodiment0.05 to 0.07 equivalents of catalyst is used per equivalent of imine. Inanother particular embodiment 0.00008 equivalents of catalyst is usedper equivalent of imine.

In certain embodiments, the reaction mixture comprising thehydridosilane reagent(s), imine reagent(s), and catalyst(s) furthercomprises an anhydrous solvent. Exemplary solvents may include, but arenot limited to linear-, branched-, cyclic- or poly-ethers (e.g.,tetrahydrofuran (THF), diethyl ether, diglyme, and/or tetraglyme);linear-, branched-, or cyclic-alkanes, alkenes, aromatics andhalocarbons (e.g. pentane, hexanes, toluene and dichloromethane). Theselection of one or more solvent, if added, may be influenced by itscompatibility with reagents contained within the reaction mixture, thesolubility of the catalyst, and/or the separation process for theintermediate product and/or the end product chosen. In otherembodiments, the reaction mixture does not comprise a solvent. In theseor other embodiments, the mixture of imine and hydridosilane reagentsmay be used as the liquid medium for the reaction in the reactionmixture. In alternative embodiments, however, the reaction mixture doesnot contain any solvent.

In the method described herein, the reaction between the hydridosilanereagent(s) and the imine reagent(s) occurs at one or more temperaturesranging from about 0° C. to about 100° C. Exemplary temperatures for thereaction include ranges having any one or more of the followingendpoints: 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100° C. Thesuitable temperature range for this reaction may be dictated by thephysical properties of the hydridosilane reagent(s), imine reagent(s),catalyst(s), and optional solvent. Examples of particular reactortemperature ranges include but are not limited to, 0° C. to 80° C. orfrom 0° C. to 30° C.

In certain embodiments of the method described herein, the pressure ofthe reaction may range from about 1 to about 115 psia or from about 15to about 45 psia. In some embodiments where the hydridosilane reagent isa liquid under ambient conditions, the reaction is run at atmosphericpressure. In some embodiments where the hydridosilane reagent is a gasunder ambient conditions, the reaction is run under above 15 psia.

In certain embodiments, one or more reagents may be introduced to thereaction mixture as a liquid or a vapor. In embodiments where one ormore of the reagents is added as a vapor, a non-reactive gas such asnitrogen or an inert gas may be employed as a carrier gas to deliver thevapor to the reaction mixture. In embodiments where one or more of thereagents is added as a liquid, the regent may be added neat, oralternatively diluted with a solvent. The reagent is fed to the reactionmixture until the desired conversion to the crude mixture containing theorganoaminosilane product, or crude liquid, has been achieved. Incertain embodiments, the reaction may be run in a continuous manner byreplenishing the hydridosilane and/or imine reagents and removing thereaction products and the crude liquid from the reactor.

An example of the catalytic hydrosiliation method described hereincomprises a combining hydridosilane and imine to provide a reactionmixture in the presence of 0.1-10 mol % catalyst under ambientconditions to produce an organoaminosilane, organoaminodisilane, ororganoaminocarbosilane compound as shown below in the following reactionscheme (1). The hydridosilane reagent having the following formulaR¹R²R³SiH wherein R¹, R² and R³ are each independently selected fromhydrogen, C₁₋₁₀ linear alkyl group, a C₃₋₁₀ branched alkyl group, aC₄₋₁₀ cyclic alkyl group, a C₂₋₁₀ alkenyl group, a C₄₋₁₀ aromatic group,a C₄₋₁₀ heterocyclic group, a C₁₋₁₀ linear organoamino group, a C₂₋₁₀branched organoamino groups, a silyl group, a C₁₋₁₀ linear carbosilylgroup, and a C₂₋₁₀ branched carbosilyl group and wherein at least oneof, or none of, R¹ and R², R¹ and R³, or R² and R³ in the hydridosilanereagent are linked to form a substituted or unsubstituted cyclic ring.

The reaction may require an excess of either hydridosilane reagent orimine to regulate the extent of hydrosilylation, and solvents such astetrahydrofuran (THF) or hexanes may be used to facilitate the reactionprogress. The hydridosilane reagents that are volatile liquids or gases[e.g. SiH₄ (silane), Si₂H₆ (disilane), MeSiH₃ (methylsilane), EtSiH₃(ethylsilane), Et₂SiH₂ (diethylsilane), PhSiH₃ (phenylsilane),H₃SiCH₂CH₂SiH₃ (1,4-disilabutane), H₃SiCH₂SiH₃ (1,3-disilapropane),H₃SiCH₂(CH₃)SiH₃ (2-methyl-1,4-disilapropane), (CH₂CH₂CH₂CH₂)SiH₂(1-silacyclopentane), (CH₂CH₂CH₂CH₂)SiHMe (1-methyl-1-silacyclopentane),(CH₂CH₂CH₂)SiH₂ (1-silacyclobutane), (CH₂SiH₂CH₂)SiH₂(1,3-disilacyclobutane)], pressures greater than 1 atmospheres (atm) maybe required to maintain sufficient levels of these reagents in theliquid phase. Once the reaction is complete or has reached equilibrium,the organoaminosilane, organoaminodisilane, or organoaminocarbosilaneproduct can be purified by distillation. Referring to the above reactionscheme (1), the final organoaminosilane, organoaminodisilane, ororganoaminocarbosilane product is formed by the reaction of the imineand hydridosilane. A >50% stoichiometric excess of hydridosilane isgenerally used to ensure complete reaction, though smaller excesses maybe used if the mixing period is adequately long

The crude mixture comprising the desired organoaminosilane,organoaminodisilane, or organoaminocarbosilane product, catalyst(s), andpotentially residual imine, residual hydridosilane, solvent(s), orundesired organoaminosilane product(s) may require separationprocess(es). Examples of suitable separation processes include, but arenot limited to, distillation, evaporation, membrane separation,filtration, vapor phase transfer, extraction, fractional distillationusing an inverted column, and combinations thereof. In particularembodiments, the crude fluid is first separated from the residualcatalyst by vacuum transfer or distillation at lower temperatures priorto isolation of the desired product by fractional distillation in orderto prevent the catalyzation of undesired reactions during thepurification process. In these embodiments, the pressure can varyconsiderably from atmospheric to full vacuum. In this embodiment orother embodiments, the reaction occurs at one or more temperaturesranging from about 20° C. to about 200° C. Exemplary temperatures forthe reaction include ranges having any one or more of the followingendpoints: 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150,160, 170, 180, 190, or 200° C. Examples of particular reactortemperature ranges include but are not limited to, 20° C. to 200° C. orfrom 70° C. to 160° C.

In certain embodiments of the method described herein, the pressure ofthe reaction may range from about 0.1 to about 115 psia or from about 10to about 45 psia. In one particular embodiment, the reaction is run at apressure of about 100 psia.

In certain preferred embodiments, the reagents in the reaction mixtureare gaseous. In these embodiments, the contact of the catalyst withreaction mixture may be defined in terms of defined by the bulk reactorvolume displaced by the catalyst÷reactant (e.g., silane and/or silicasource gas) gas flow rate. The gas-catalyst contact time may range fromabout 5 to about 200 seconds. Exemplary times for the contact of thereactive mixture with the catalyst include ranges having any one or moreof the following endpoints: 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100,110, 120, 130, 140, 150, 160, 170, 180, 190, or 200 seconds. Examples ofparticular contact time ranges include but are not limited to, 20 to 100or from 10 to 40 seconds.

Exemplary catalysts that can be used with the method described hereininclude, but are not limited to the following: alkaline earth metalcatalysts; halide-free main group, transition metal, lanthanide, andactinide catalysts; and halide-containing main group, transition metal,lanthanide, and actinide catalysts.

Exemplary alkaline earth metal catalysts include but are not limited tothe following: Mg[N(SiMe₃)₂]₂, To^(M)MgMe[To^(M)=tris(4,4-dimethyl-2-oxazolinyl)phenylborate], To^(M)Mg—H,To^(M)Mg—NR₂ (R=H, alkyl, aryl) Ca[N(SiMe₃)₂]₂, [(dipp-nacnac)CaX(THF)]₂(dipp-nacnac=CH[(CMe)(2,6-^(i)Pr₂-C₆H₃N)]₂; X=H, alkyl, carbosilyl,organoamino), Ca(CH₂Ph)₂, Ca(C₃H₅)₂, Ca(α-Me₃Si-2-(Me₂N)-benzyl)₂(THF)₂,Ca(9-(Me₃Si)-fluorenyl)(α-Me₃Si-2-(Me₂N)-benzyl)(THF),[(Me₃TACD)₃Ca₃(μ³-H)₂]⁺ (Me₃TACD=Me₃[12]aneN₄), Ca(η²-Ph₂CNPh)(hmpa)₃(hmpa=hexamethylphosphoramide), Sr[N(SiMe₃)₂]₂, and other M²⁺ alkalineearth metal-amide, -imine, -alkyl, -hydride, and -carbosilyl complexes(M=Ca, Mg, Sr, Ba).

Exemplary halide-free, main group, transition metal, lanthanide, andactinide catalysts include but are not limited to the following:1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene, 2,2′-bipyridyl,phenanthroline, B(C₆F₅)₃, BR₃ (R=linear, branched, or cyclic C₁ to C₁₀alkyl group, a C₅ to C₁₀ aryl group, or a C₁ to C₁₀ alkoxy group), AIR₃(R=linear, branched, or cyclic C₁ to C₁₀ alkyl group, a C₅ to C₁₀ arylgroup, or a C₁ to C₁₀ alkoxy group), (C₅H₅)₂TiR₂ (R=alkyl, H, alkoxy,organoamino, carbosilyl), (C₅H₅)₂Ti(OAr)₂ [Ar=(2,6-(^(i)Pr)₂C₆H₃)],(C₅H₅)₂Ti(SiHRR′)PMe₃ (wherein R, R′ are each independently selectedfrom H, Me, Ph), TiMe₂(dmpe)₂ (dmpe=1,2-bis(dimethylphosphino)ethane),bis(benzene)chromium(0), Cr(CO)₆, Mn₂(CO)₁₂, Fe(CO)₅, Fe₃(CO)₁₂,(C₅H₅)Fe(CO)₂Me, Co₂(CO)₈, Ni(II) acetate, Nickel(II) acetylacetonate,Ni(cyclooctadiene)₂, [(dippe)Ni(μ-H)]₂(dippe=1,2-bis(diisopropylphosphino)ethane), (R-indenyl)Ni(PR′₃)Me(R=1-^(i)Pr, 1-SiMe₃, 1,3-(SiMe₃)₂; R′=Me,Ph),[{Ni(η-CH₂:CHSiMe₂)₂O}₂{μ-(η-CH₂:CHSiMe₂)₂O}], Cu(I) acetate, CuH,[tris(4,4-dimethyl-2-oxazolinyl)phenylborate]ZnH, (C₅H₅)₂ZrR₂ (R=alkyl,H, alkoxy, organoamino, carbosilyl), Ru₃(CO)₁₂,[(Et₃P)Ru(2,6-dimesitylthiophenolate)][B[3,5-(CF₃)₂C₆H₃]₄],[(C₅Me₅)Ru(R₃P)_(x)(NCMe)_(3-x)]⁺ (wherein R is selected from a linear,branched, or cyclic C₁ to C₁₀ alkyl group and a C₅ to C₁₀ aryl group;x=0, 1, 2, 3), Rh₆(CO)₁₆, tris(triphenylphosphine)rhodium(I)carbonylhydride, Rh₂H₂(CO)₂(dppm)₂ (dppm=bis(diphenylphosphino)methane,Rh₂(μ-SiRH)₂(CO)₂(dppm)₂ (R=Ph, Et, C₆H₁₃), Pd/C,tris(dibenzylideneacetone)dipalladium(0),tetrakis(triphenylphosphine)palladium(0), Pd(II) acetate, (C₅H₅)₂SmH,(C₅Me₅)₂SmH, (THF)₂Yb[N(SiMe₃)₂]₂, (NHC)Yb(N(SiMe₃)₂)₂[NHC=1,3-bis(2,4,6-trimethylphenyl) imidazol-2-ylidene)],Yb(η²-Ph₂CNPh)(hmpa)₃ (hmpa=hexamethylphosphoramide), W(CO)₆, Re₂(CO)₁₀,Os₃(CO)₁₂, Ir₄(CO)₁₂, (acetylacetonato)dicarbonyliridium(I),Ir(Me)₂(C₅Me₅)L (L=PMe₃, PPh₃), [Ir(cyclooctadiene)OMe]₂, PtO₂ (Adams'scatalyst), Pt/C, Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane(Karstedt's catalyst), bis(tri-tert-butylphosphine)platinum(0),Pt(cyclooctadiene)₂, [(Me₃Si)₂N]₃U][BPh₄], [(Et₂N)₃U][BPh₄], and otherhalide-free M^(n+) complexes (M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn,Y, Zr, Nb, Mo, Ru, Rh, Pd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho,Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, U; n=0, 1, 2, 3, 4, 5, 6).

Exemplary halide-containing, main group, transition metal, lanthanide,and actinide catalysts include but are not limited to the following: BX₃(X=F, Cl, Br, I), BF₃.OEt₂, AIX₃ (X=F, Cl, Br, I), (C₅H₅)₂TiX₂ (X=F,Cl), [Mn(CO)₄Br]₂, NiCl₂, (C₅H₅)₂ZrX₂ (X=F, Cl), PdCl₂, PdI₂, CuCl, CuI,CuF₂, CuCl₂, CuBr₂, Cu(PPh₃)₃Cl, ZnCl₂, [(C₆H₆)RuX₂]₂ (X=Cl, Br, I),(Ph₃P)₃RhCl (Wilkinson's catalyst), [RhCl(cyclooctadiene)]₂,di-p-chloro-tetracarbonyldirhodium(I), bis(triphenylphosphine)rhodium(I)carbonyl chloride, NdI₂, SmI₂, DyI₂, (POCOP)IrHCl(POCOP=2,6-(R₂PO)₂C₆H₃; R=^(i)Pr, ^(n)Bu, Me), H₂PtCl₆.nH₂O (Speier'scatalyst), PtCl₂, Pt(PPh₃)₂Cl₂, and other halide-containing M^(n+)complexes (M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru,Rh, Pd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf,Ta, W, Re, Os, Ir, Pt, U; n=0, 1, 2, 3, 4, 5, 6).

In certain embodiments, the compounds, or organoaminosilanes,organoaminodisilanes, and organoaminocarbosilanes, prepared using themethods described herein and compositions comprising the compounds arepreferably substantially free of halide ions. As used herein, the term“substantially free” as it relates to halide ions (or halides) such as,for example, chlorides and fluorides, bromides, and iodides, means lessthan 5 ppm (by weight), preferably less than 3 ppm, and more preferablyless than 1 ppm, and most preferably 0 ppm. Compositions according tothe present invention that are substantially free of halides can beachieved by (1) reducing or eliminating chloride sources during chemicalsynthesis, and/or (2) implementing an effective purification process toremove chloride from the crude product such that the final purifiedproduct is substantially free of halides. Halide sources may be reducedduring synthesis by using reagents that do not contain halides such asthe halide-free catalysts described herein. In a similar manner, thesynthesis should not use halide based solvents, catalysts, or solventswhich contain unacceptably high levels of halide contamination.Alternatively, or additionally, the crude product may also be treated byvarious purification methods to render the final product substantiallyfree of halides such as chlorides. Such methods are well described inthe prior art and, may include, but are not limited to, purificationprocesses such as distillation, or adsorption. Distillation is commonlyused to separate impurities from the desire product by exploitingdifferences in boiling point. Adsorption may also be used to takeadvantage of the differential adsorptive properties of the components toeffect separation such that the final product is substantially free ofhalide. Adsorbents such as, for example, commercially available solidbases can be used to remove halides such as chloride.

The following Table 1 lists imines that can be used as reagents in themethod described herein to provide exemplary organoaminosilanes,organoaminodisilanes, organoaminocarbosilanes, and organoaminescompounds defined herein.

TABLE 1 Exemplary imines

N-iso-propylidene- N-sec-butylidene- methylamine methylamine

N-cyclohexylidene- N-cyclopentylidene- methylamine methylamine

N-iso-propylidene- N-sec-butylidene- ethylamine ethylamine

N-cyclohexylidene- N-cyclopenytlidene- ethylamine ethylamine

N-iso-propyldiene-n- N-sec-butylidene-n- propylamine propylamine

N-cyclohexylidene-n- N-cyclopentylidene-n- propylamine propylamine

N-iso-propylidene-iso- N-sec-butylidene-iso- propylamine propylamine

N-cyclohexylidene-iso- N-cyclopentylidene-iso- propylamine propylamine

N-iso-propylidene-sec- N-sec-butylidene-sec- butylamine butylamine

N-cyclohexylidene-sec- N-cyclopentylidene-sec- butylamine butylamine

N-iso-propylidene-tert- N-sec-butylidene-tert- butylamine butylamine

N-cyclohexylidene-tert- N-cyclopentylidene-tert- butylamine butylamine

N-iso-propylidene- N-sec-butylidene- cyclohexylamine cyclohexylamine

N-cyclohexylidene- N-cyclopentylidene- cyclohexylamine cyclohexylamine

N-iso-propylidene- N-sec-butylidene- phenylamine phenylamine

N-cyclohexylidene- N-cyclopentylidene- phenylamine phenylamine

N-ethylidene- N-methylidene- phenylamine methylamine

N-ethylidene- N-n-propylidene-n- ethylamine propylamine

TABLE 2 Exemplary Organoaminosilane Compounds

N-methyl-N-iso- N-sec-butyl-N- propylaminosilane methylaminosilane

N-cyclohexyl-N- N-methyl-N- methylaminosilane cyclopentylaminosilane

N-ethyl-N-iso- N-sec-butyl-N- propylaminosilane ethylaminosilane

N-ethyl-N- N-ethyl-N- cyclohexylaminosilane cyclopentylaminosilane

N-n-propyl-N-iso- N-sec-butyl-N-n- propylaminosilane propylaminosilane

N-cyclohexyl-N-n- N-cyclopentyl-N-n- propylaminosilane propylaminosilane

N,N-di-iso- N-sec-butyl-N-iso- propylaminosilane propylaminosilane

N-cyclohexyl-N-iso- N-cyclopentyl-N-iso- propylaminosilanepropylaminosilane

N,N-di-sec-butylaminosilane N-sec-butyl-N- cyclohexylaminosilane

N-sec-butyl-N- N-tertbutyl-N-iso- cyclopentylaminosilanepropylaminosilane

N-sec-butyl-N-tert- N-tert-butyl-N- butylaminosilanecyclohexylaminosilane

N-tert-butyl-N- N,N-dicyclohexylaminosilane cyclopentylaminosilane

N-cyclohexyl-N- N-phenyl-N-iso- cyclopentylaminosilane propylaminosilane

N-sec-butyl-N- N-cyclohexyl-N- phenylaminosilane phenylaminosilane

N-cyclopentyl-N- N-ethyl-N- phenylaminosilane phenylaminosilane

N,N-dimethylaminosilane N,N-diethylaminosilane

N,N-di-n-propylaminosilane

TABLE 3 Exemplary Organoaminodisilane Compounds

N-methyl-N-iso- N-sec-butyl-N- propylaminodisilane methylaminodisilane

N-cyclohexyl-N- N-methyl-N- methylaminodisilane cyclopentylaminodisilane

N-ethyl-N-iso- N-sec-butyl-N- propylaminodisilane ethylaminodisilane

N-ethyl-N- N-ethyl-N- cyclohexylaminodisilane cyclopentylaminodisilane

N-n-propyl-N-iso- N-sec-butyl-N-n- propylaminodisilanepropylaminodisilane

N-cyclohexyl-N-n- N-cyclopentyl-N-n- propylaminodisilanepropylaminodisilane

N,N-di-iso- N-sec-butyl-N-iso- propylaminodisilane propylaminodisilane

N-cyclohexyl-N-iso- N-cyclopentyl-N-iso- propylaminodisilanepropylaminodisilane

N,N-di-sec- N-sec-butyl-N- butylaminodisilane cyclohexylaminodisilane

N-sec-butyl-N- N-tert-butyl-N-iso- cyclopentylaminodisilanepropylaminodisilane

N-sec-butyl-N-tert- N-tert-butyl-N- butylaminodisilanecyclohexylaminodisilane

N-tert-butyl-N- N,N- cyclopentylaminodisilane dicyclohexylaminodisilane

N-cyclohexyl-N- N-phenyl-N-iso- cyclopentylaminodisilanepropylaminodisilane

N-sec-butyl-N- N-cyclohexyl-N- phenylaminodisilane phenylaminodisilane

N-cyclopentyl-N- N-ethyl-N- phenylaminodisilane phenylaminodisilane

N,N-dimethylaminodisilane N,N-diethylaminodisilane

N,N-di-n-propylaminodisilane

TABLE 4 Exemplary Organoaminodisilane (more specifically 1,2-bis(organoamino)disilane) Compounds

1,2-bis(N-methyl-N-iso- 1,2-bis(N-sec-butyl-N- propylamino)disilanemethylamino)disilane

1,2-bis(N-cyclohexyl-N- 1,2-bis(N-methyl-N- methylamino)disilanecyclopentylamino)disilane

1,2-bis(N-ethyl-N-iso- 1,2-bis(N-sec-butyl-N- propylamino)disilaneethylamino)disilane

1,2-bis(N-ethyl-N- 1,2-bis(N-ethyl-N- cyclohexylamino)disilanecyclopentylamino)disilane

1,2-bis(N-n-propyl-N-iso- 1,2-bis(N-sec-butyl-N-n- propylamino)disilanepropylamino)disilane

1,2-bis(N-cyclohexyl-N-n- 1,2-bis(N-cyclopentyl-N-n-propylamino)disilane propylamino)disilane

1,2-bis(N,N-di-iso- 1,2-bis(N-sec-butyl-N-iso- propylamino)disilanepropylamino)disilane

1,2-bis(N-cyclohexyl-N-iso- 1,2-bis(N-cyclopentyl-N-iso-propylamino)disilane propylamino)disilane

1,2-bis(N,N-di-sec- 1,2-bis(N-sec-butyl-N- butylamino)disilanecyclohexylamino)disilane

1,2-bis(N-sec-butyl-N- 1,2-bis(N-tert-butyl-N-iso-cyclopentylamino)disilane propylamino)disilane

1,2-bis(N-sec-butyl-N-tert- 1,2-bis(N-tert-butyl-N- butylamino)disilanecyclohexylamino)disilane

1,2-bis(N-tert-butyl-N- 1,2-bis(N,N- cyclopentylamino)disilanedicyclohexylamino)disilane

1,2-bis(N-cyclohexyl-N- 1,2-bis(N-phenyl-N-iso-cyclopentylamino)disilane propylamino)disilane

1,2-bis(N-sec-butyl-N- 1,2-bis(N-cyclohexyl-N- phenylamino)disilanephenylamino)disilane

1,2-bis(N-cyclopentyl-N- 1,2-bis(N-ethyl-N- phenylamino)disilanephenylamino)disilane

1,2-bis(N,N- 1,2-bis(N,N- dimethylamino)disilane dieethylamino)disilane

1,2-bis(N,N-di-n- propylamino)disilane

TABLE 5 Exemplary Organoaminocarbosilane (more specificallyorganoamino-1,4- disilabutane) Compounds

1-(N-methyl-N-iso- 1-(N-sec-butyl-N- propylamino)-1,4-disilabutanemethylamino)-1,4-disilabutane

1-(N-cyclohexyl-N- 1-(N-methyl-N- methylamino)-1,4-disilabutanecyclopentylamino)-1,4- disilabutane

1-(N-ethyl-N-iso-propylamino)- 1-(N-sec-butyl-N- 1,4-disilabutaneethylamino)-1,4-disilabutane

1-(N-ethyl-N-cyclohexylamino)- 1-(N-ethyl-N-cyclopentylamino)-1,4-disilabutane 1,4-disilabutane

1-(N-n-propyl-N-iso- 1-(N-sec-butyl-N-n- propylamino)-1,4-disilabutanepropylamino)-1,4-disilabutane

1-(N-cyclohexyl-N-n- 1-(N-cyclopentyl-N-n- propylamino)-1,4-disilabutanepropylamino)-1,4-disilabutane

1-(N,N-di-iso-propylamino)- 1-(N-sec-butyl-N-iso- 1,4-disilabutanepropylamino)-1,4- disilabutane

1-(N-cyclohexyl-N-iso- 1-(N-cyclopentyl-N-iso-propylamino)-1,4-disilabutane propylamino)-1,4-disilabutane

1-(N,N-di-sec-butylamino)-1,4- 1-(N-sec-butyl-N- disilabutanecyclohexylamino)-1,4- disilabutane

1-(N-sec-butyl-N- 1-(N-tert-butyl-N-iso- cyclopentylamino)-1,4-propylamino)-1,4-disilabutane disilabutane

1-(N-sec-butyl-N-tert- 1-(N-tert-butyl-N- butylamino)-1,4-disilabutanecyclohexylamino)-1,4- disilabutane

1-(N-tert-butyl-N- 1-(N,N-dicyclohexylamino)-1,4- cyclopentylamino)-1,4-disilabutane disilabutane

1-(N-cyclohexyl-N- 1-(N-phenyl-N-iso- cyclopentylamino)-1,4-propylamino)-1,4- disilabutane disilabutane

1-(N-sec-butyl-N- 1-(N-cyclohexyl-N- phenylamino)-1,4-disilabutanephenylamino)-1,4-disilabutane

1-(N-cyclopentyl-N- 1-(N-ethyl-N-phenylamino)-phenylamino)-1,4-disilabutane 1,4-disilabutane

1-(N,N-dimethylamino)-1,4- 1-(N,N-diethylamino)-1,4- disilabutanedisilabutane

1-(N,N-di-n-propylamino)-1,4- disilabutane

TABLE 6 Exemplary Organoaminocarbosilane (more specifically1,4-bis(organoamino)- 1,4-disilabutane) Compounds

1,4-bis(N-methyl-N-iso- 1,4-bis(N-sec-butyl-N-propylamino)-1,4-disilabutane methylamino)-1,4- disilabutane

1,4-bis(N-cyclohexyl-N- 1,4-bis(N-methyl-N-methylamino)-1,4-disilabutane cyclopentylamino)-1,4- disilabutane

1,4-bis(N-ethyl-N-iso- 1,4-bis(N-sec-butyl-N-propylamino)-1,4-disilabutane ethylamino)-1,4-disilabutane

1,4-bis(N-ethyl-N- 1,4-bis(N-ethyl-N- cyclohexylamino)-1,4-cyclopentylamino)-1,4- disilabutane disilabutane

1,4-bis(N-n-propyl-N-iso- 1,4-bis(N-sec-butyl-N-n-propylamino)-1,4-disilabutane propylamino)-1,4- disilabutane

1,4-bis(N-cyclohexyl-N-n- 1,4-bis(N-cyclopentyl-N-n-propylamino)-1,4-disilabutane propylamino)-1,4-disilabutane

1,4-bis(N,N-di-iso- 1,4-bis(N-sec-butyl-N-iso-propylamino)-1,4-disilabutane propylamino)-1,4- disilabutane

1,4-bis(N-cyclohexyl-N-iso- 1,4-bis(N-cyclopentyl-N-iso-propylamino)-1,4-disilabutane propylamino)-,4-disilabutane

1,4-bis(N,N-di-sec- 1,4-bis(N-sec-butyl-N- butylamino)-1,4-disilabutanecyclohexylamino)-1,4- disilabutane

1,4-bis(N-sec-butyl-N- 1,4-bis(N-tert-butyl-N-iso-cyclopentylamino)-1,4- propylamino)-1,4-disilabutane disilabutane

1,4-bis(N-sec-butyl-N-tert- 1,4-bis(N-tert-butyl-N-butylamino)-1,4-disilabutane cyclohexylamino)-1,4- disilabutane

1,4-bis(N-tert-butyl-N- 1,4-bis(N,N-dicyclohexylamino)-cyclopentylamino)-1,4- 1,4-disilabutane disilabutane

1,4-bis(N-cyclohexyl-N- 1,4-bis(N-phenyl-N-iso- cyclopentylamino)-1,4-propylamino)-1,4- disilabutane disilabutane

1,4-bis(N-sec-butyl-N- 1,4-bis(N-cyclohexyl-N-phenylamino)-1,4-disilabutane phenylamino)-1,4-disilabutane

1,4-bis(N-cyclopentyl-N- 1,4-bis(N-ethyl-N-phenylamino)-1,4-disilabutane phenylamino)-1,4- disilabutane

1,4-bis(N,N-dimethylamino)- 1,4-bis(N,N-diethylamino)-1,4-phenylamino)-1,4- 1,4-disilabutane

1,4-bis(N,N-di-n-propylamino)- 1,4-disilabutane

TABLE 7 Exemplary Organoaminocarbosilane (more specificallyorganoamino-1,3- disilapropane) Compounds

1-(N-methyl-N-iso- 1-(N-sec-butyl-N- propylamino)-1,3- methylamino)-1,3-disilapropane disilapropane

1-(N-cyclohexyl-N- 1-(N-methyl-N- methylamino)-1,3-cyclopentylamino)-1,3- disilapropane disilapropane

1-(N-ethyl-N-iso-propylamino)- 1-(N-sec-butyl-N- 1,3-disilapropaneethylamino)-1,3- disilapropane

1-(N-ethyl-N-cyclohexylamino)- 1-(N-ethyl-N-cyclopentylamino)-1,3-disilapropane 1,3-disilapropane

1-(N-n-propyl-N-iso- 1-(N-sec-butyl-N-n- propylamino)-1,3-propylamino)-1,3- disilapropane disilapropane

1-(N-cyclohexyl-N-n- 1-(N-cyclopentyl-N-n-propylamino)-1,3-disilapropane propylamino)-1,3-disilapropane

1-(N,N-di-iso-propylamino)- 1-(N-sec-butyl-N-iso- 1,3-disilapropanepropylamino)-1,3- disilapropane

1-(N-cyclohexyl-N-iso- 1-(N-cyclopentyl-N-iso-propylamino)-1,3-disilapropane propylamino)-1,3-disilapropane

1-(N,N-di-sec-butylamino)-1,3- 1-(N-sec-butyl-N- disilapropanecyclohexylamino)-1,3- disilapropane

1-(N-sec-butyl-N- 1-(N-tert-butyl-N- cyclopentylamino)-1,3-isopropylamino)-1,3- disilapropane disilapropane

1-(N-sec-butyl-N- 1-(N-tert-butyl-N- tertbutylamino)-1,3-cyclohexylamino)-1,3- disilapropane disilapropane

1-(N-tert-butyl-N- 1-(N,N-dicyclohexylamino)-1,3- cyclopentylamino)-1,3-disilapropane disilapropane

1-(N-cyclohexyl-N- 1-(N-phenyl-N-iso- cyclopentylamino)-1,3-propylamino)-1,3- disilapropane disilapropane

1-(N-sec-butyl-N- 1-(N-cyclohexyl-N- phenylamino)-1,3-phenylamino)-1,3-disilapropane disilapropane

1-(N-cyclopentyl-N- 1-(N-ethyl-N-phenylamino)- phenylamino)-1,3-1,3-disilapropane disilapropane

1-(N,N-dimethylamino)-1,3- 1-(N,N-dimethylamino)-1,3- disilapropanedisilapropane

1-(N,N-di-n-propylamino)-1,3- disilapropane

TABLE 8 Exemplary Organoaminocarbosilane (more specifically1,3-bis(organoamino)- 1,3-disilapropane) Compounds

1,3-bis(N-methyl-N-iso- 1,3-bis(N-sec-butyl-N- propylamino)-1,3-methylamino)-1,3- disilapropane disilapropane

1,3-bis(N-cyclohexyl-N- 1,3-bis(N-methyl-N- methylamino)-1,3-cyclopentylamino)-1,3- disilapropane disilapropane

1,3-bis(N-ethyl-N-iso- 1,3-bis(N-sec-butyl-N- propylamino)-1,3-ethylamino)-1,3- disilapropane disilapropane

1,3-bis(N-ethyl-N- 1,3-bis(N-ethyl-N- cyclohexylamino)-1,3-cyclopentylamino)-1,3- disilapropane disilapropane

1,3-bis(N-n-propyl-N-iso- 1,3-bis(N-sec-butyl-N-n- propylamino)-1,3-propylamino)-1,3- disilapropane disilapropane

1,3-bis(N-cyclohexyl-N-n- 1,3-bis(N-cyclopentyl-N-n-propylamino)-1,3-disilapropane propylamino)-1,3-disilapropane

1,3-bis(N,N-di-iso- 1,3-bis(N-sec-butyl-N-iso- propylamino)-1,3-propylamino)-1,3- disilapropane disilapropane

1,3-bis(N-cyclohexyl-N-iso- 1,3-bis(N-cyclopentyl-N-iso-propylamino)-1,3-disilapropane propylamino)-1,3-disilapropane

1,3-bis(N,N-di-sec- 1,3-bis(N-sec-butyl-N- butylamino)-1,3-disilapropanecyclohexylamino)-1,3- disilapropane

1,3-bis(N-sec-butyl-N- 1,3-bis(N-tert-butyl-N-iso-cyclopentylamino)-1,3- propylamino)-1,3-disilapropane disilapropane

1,3-bis(N-sec-butyl-N-tert- 1,3-bis(N-tert-butyl-N-butylamino)-1,3-disilapropane cyclohexylamino)-1,3- disilapropane

1,3-bis(N-tert-butyl-N- 1,3-bis(N,N-dicyclohexylamino)-cyclopentylamino)-1,3- 1,3-disilapropane disilapropane

1,3-bis(N-cyclohexyl-N- 1,3-bis(N-phenyl-N-iso- cyclopentylamino)-1,3-propylamino)-1,3- disilapropane disilapropane

1,3-bis(N-sec-butyl-N- 1,3-bis(N-cyclohexyl-N- phenylamino)-1,3-phenylamino)-1,3-disilapropane disilapropane

1,3-bis(N-cyclopentyl-N- 1,3-bis(N-ethyl-N- phenylamino)-1,3-phenylamino)-1,3- disilapropane disilapropane

1,3-bis(N,N-dimethylamino)- 1,3-bis(N,N-diethylamino)-1,3-1,3-disilapropane disilapropane

1,3-bis(N,N-di-n-propylamino)- 1,3-disilapropane

TABLE 9 Exemplary Organoaminocarbosilane (more specifically1-organoamino-2- methyl-1,3-disilapropane) Compounds

1-(N-methyl-N-iso- 1-(N-sec-butyl-N- propylamino)-2-methyl-1,3-methylamino)-2-methyl-1,3- disilapropane disilapropane

1-(N-cyclohexyl-N- 1-(N-methyl-N- methylamino)-2-methyl-1,3-cyclopentylamino)-2-methyl-1,3- disilapropane disilapropane

1-(N-ethyl-N-iso-propylamino)- 1-(N-sec-butyl-N-2-methyl-1,3-disilapropane ethylamino)-2-methyl-1,3- disilapropane

1-(N-ethyl-N-cyclohexylamino)- 1-(N-ethyl-N-cyclopentylamino)-2-methyl-1,3-disilapropane 2-methyl-1,3-disilapropane

1-(N-n-propyl-N-iso- 1-(N-sec-butyl-N-n- propylamino)-2-methyl-1,3-propylamino)-2-methyl-1,3- disilapropane disilapropane

1-(N-cyclohexyl-N-n- 1-(N-cyclopentyl-N-n- propylamino)-2-methyl-1,3-propylamino)-2-methyl-1,3- disilapropane disilapropane

1-(N,N-di-iso-propylamino)-2- 1-(N-sec-butyl-N-iso-methyl-1,3-disilapropane propylamino)-2-methyl-1,3- disilapropane

1-(N-cyclohexyl-N-iso- 1-(N-cyclopentyl-N-iso-propylamino)-2-methyl-1,3- propylamino)-2-methyl-1,3- disilapropanedisilapropane

1-(N,N-di-sec-butylamino)-2- 1-(N-sec-butyl-N- methyl-1,3-disilapropanecyclohexylamino)-2-methyl- 1,3-disilapropane

1-(N-sec-butyl-N- 1-(N-tert-butyl-N-iso- cyclopentylamino)-2-methyl-propylamino)-2-methyl-1,3- 1,3-disilapropane disilapropane

1-(N-sec-butyl-N-tert- 1-(N-tert-butyl-N- butylamino)-2-methyl-1,3-cyclohexylamino)-2-methyl- disilapropane 1,3-disilapropane

1-(N-tert-butyl-N- 1-(N,N-dicyclohexylamino)-2-cyclopentylamino)-2-methyl- methyl-1,3-disilapropane 1,3-disilapropane

1-(N-cyclohexyl-N- 1-(N-phenyl-N-iso- cyclopentylamino)-2-methyl-propylamino)-2-methyl-1,3- 1,3-disilapropane disilapropane

1-(N-sec-butyl-N- 1-(N-cyclohexyl-N- phenylamino)-2-methyl-1,3-phenylamino)-2-methyl-1,3- disilapropane disilapropane

1-(N-cyclopentyl-N- 1-(N-ethyl-N-phenylamino)-phenylamino)-2-methyl-1,3- 2-methyl-1,3-disilapropane disilapropane

1-(N,N-dimethylamino)-2- 1-(N,N-dimethylamino)-2-methyl-1,3-disilapropane methyl-1,3-disilapropane

1-(N,N-di-n-propylamino)-2- methyl-1,3-disilapropane

TABLE 10 Exemplary Organoaminocarbosilane (more specifically1,3-bis(organoamino)-2-methyl-1,3-disilapropane) Compounds

  1,3-bis(N-methyl-N-iso- propylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-sec-butyl-N- methylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-cyclohexyl-N- methylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-methyl-N- cyclopentylamino)-2-methyl- 1,3-disilapropane

  1,3-bis(N-ethyl-N-iso- propylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-sec-butyl-N- ethylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-ethyl-N- cyclohexylamino)-2-methyl- 1,3-disilapropane

  1,3-bis(N-ethyl-N- cyclopentylamino)-2-methyl- 1,3-disilapropane

  1,3-bis(N-n-propyl-N-iso- propylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-sec-butyl-N-n- propylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-cyclohexyl-N-n- propylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-cyclopentyl-N-n- propylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N,N-di-iso- propylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-sec-butyl-N-iso- propylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-cyclohexyl-N-iso- propylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-cyclopentyl-N-iso- propylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N,N-di-sec- butylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-sec-butyl-N- cyclohexylamino)-2-methyl- 1,3-disilapropane

  1,3-bis(N-sec-butyl-N- cyclopentylamino)-2-methyl- 1,3-disilapropane

  1,3-bis(N-tert-butyl-N-iso- propylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-sec-butyl-N-tert- butylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-tert-butyl-N- cyclohexylamino)-2-methyl- 1,3-disilapropane

  1,3-bis(N-tert-butyl-N- cyclopentylamino)-2-methyl- 1,3-disilapropane

  1,3-bis(N,N-dicyclohexylamino)- 2-methyl-1,3-disilapropane

  1,3-bis(N-cyclohexyl-N- cyclopentylamino)-2-methyl- 1,3-disilapropane

  1,3-bis(N-phenyl-N-iso- propylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-sec-butyl-N- phenylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-cyclohexyl-N- phenylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-cyclopentyl-N- phenylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N-ethyl-N- phenylamino)-2-methyl-1,3- disilapropane

  1,3-bis(N,N-dimethylamino)-2- methyl-1,3-disilapropane

  1,3-bis(N,N-diethylamino)-2- methyl-1,3-disilapropane

  1,3-bis(N,N-di-n-propylamino)- 2-methyl-1,3-disilapropane

TABLE 11 Exemplary Organoaminocarbosilane (more specificallyorganoamino- silacyclopentane) Compounds

  1-(N-methyl-N-iso- propylamino)-silacyclopentane

  1-(N-sec-butyl-N- methylamino)- silacyclopentane

  1-(N-cyclohexyl-N- methylamino)-silacyclopentane

  1-(N-methyl-N- cyclopentylamino)- silacyclopentane

  1-(N-ethyl-N-iso-propylamino)- silacyclopentane

  1-(N-sec-butyl-N- ethylamino)- silacyclopentane

  1-(N-ethyl-N-cyclohexylamino)- silacyclopentane

  1-(N-ethyl-N-cyclopentylamino)- silacyclopentane

  1-(N-n-propyl-N-iso- propylamino)-silacyclopentane

  1-(N-sec-butyl-N-n- propylamino)- silacyclopentane

  1-(N-cyclohexyl-N-n- propylamino)-silacyclopentane

  1-(N-cyclopentyl-N-n- propylamino)-silacyclopentane

  1-(N,N-di-iso-propylamino)- silacyclopentane

  1-(N-sec-butyl-N-iso- propylamino)- silacyclopentane

  1-(N-cyclohexyl-N-iso- propylamino)-silacyclopentane

  1-(N-cyclopentyl-N-iso- propylamino)-silacyclopentane

  1-(N,N-di-sec-butylamino)- silacyclopentane

  1-(N-sec-butyl-N- cyclohexylamino)- silacyclopentane

  1-(N-sec-butyl-N- cyclopentylamino)- silacyclopentane

  1-(N-tert-butyl-N-iso- propylamino)-silacyclopentane

  1-(N-sec-butyl-N-tert- butylamino)-silacyclopentane

  1-(N-tert-butyl-N- cyclohexylamino)- silacyclopentane

  1-(N-tert-butyl-N- cyclopentylamino)- silacyclopentane

  1-(N,N-dicyclohexylamino)- silacyclopentane

  1-(N-cyclohexyl-N- cyclopentylamino)- silacyclopentane

  1-(N-phenyl-N-iso- propylamino)- silacyclopentane

  1-(N-sec-butyl-N- phenylamino)-silacyclopentane

  1-(N-cyclohexyl-N- phenylamino)-silacyclopentane

  1-(N-cyclopentyl-N- phenylamino)-silacyclopentane

  1-(N-ethyl-N-phenylamino)- silacyclopentane

  1-(N,N-dimethylamino)- silacyclopentane

  1-(N,N-diethylamino)- silacyclopentane

  1-(N,N-di-n-propylamino)- silacyclopentane

TABLE 12 Exemplary Organoaminocarbosilane (more specificallyorganoamino- methylsilacyclopentane) Compounds

  1-(N-methyl-N-iso- propylamino)-1-methyl- silacyclopentane

  1-(N-sec-butyl-N- methylamino)-1-methyl- silacyclopentane

  1-(N-cyclohexyl-N- methylamino)-1-methyl- silacyclopentane

  1-(N-methyl-N- cyclopentylamino)-1-methyl- silacyclopentane

  1-(N-ethyl-N-iso-propylamino)- 1-methyl-silacyclopentane

  1-(N-sec-butyl-N- ethylamino)-1-methyl- silacyclopentane

  1-(N-ethyl-N-cyclohexylamino)- 1-methyl-silacyclopentane

  1-(N-ethyl-N-cyclopentylamino)- 1-methyl-silacyclopentane

  1-(N-n-propyl-N-iso- propylamino)-1-methyl- silacyclopentane

  1-(N-sec-butyl-N-n- propylamino)-1-methyl- silacyclopentane

  1-(N-cyclohexyl-N-n- propylamino)-1-methyl- silacyclopentane

  1-(N-cyclopentyl-N-n- propylamino)-1-methyl- silacylopentane

  1-(N,N-di-iso-propylamino)-1- methyl-silacyclopentane

  1-(N-sec-butyl-N-iso- propylamino)-1-methyl- silacyclopentane

  1-(N-cyclohexyl-N-iso- propylamino)-1-methyl- silacyclopentane

  1-(N-cyclopentyl-N-iso- propylamino)-1-methyl- silacyclopentane

  1-(N,N-di-sec-butylamino)-1- methyl-silacyclopentane

  1-(N-sec-butyl-N- cyclohexylamino)-1-methyl- silacyclopentane

  1-(N-sec-butyl-N- cyclopentylamino)-1-methyl- silacyclopentane

  1-(N-tert-butyl-N-iso- propylamino)-1-methyl- silacyclopentane

  1-(N-sec-butyl-N-tert- butylamino)-1-methyl- silacyclopentane

  1-(N-tert-butyl-N- cyclohexylamino)-1-methyl- silacyclopentane

  1-(N-tert-butyl-N- cyclopentylamino)-1-methyl- silacyclopentane

  1-(N,N-dicyclohexylamino)-1- methyl-silacyclopentane

  1-(N-cyclohexyl-N- cyclopentylamino)-1-methyl- silacyclopentane

  1-(N-phenyl-N-iso- propylamino)-1-methyl- silacyclopentane

  1-(N-sec-butyl-N- phenylamino)-1-methyl- silacyclopentane

  1-(N-cyclohexyl-N- phenylamino)-1-methyl- silacyclopentane

  1-(N-cyclopentyl-N- phenylamino)-1-methyl- silacyclopentane

  1-(N-ethyl-N-phenylamino)- 1-methyl-silacyclopentane

  1-(N,N-dimethylamino)-1- methyl-silacyclopentane

  1-(N,N-dimethylamino)-1- methyl-silacyclopentane

  1-(N,N-di-n-propylamino)-1- methyl-silacyclopentane

TABLE 13 Exemplary Organoaminocarbosilane (more specificallyorganoamino- silacyclobutane having cyclic four-membered ring) Compounds

  1-(N-methyl-N-iso- propylamino)-silacyclobutane

  1-(N-sec-butyl-N- methylamino)- silacyclobutane

  1-(N-cyclohexyl-N- methylamino)-silacyclobutane

  1-(N-methyl-N- cyclopentylamino)- silacyclobutane

  1-(N-ethyl-N-iso-propylamino)- silacyclobutane

  1-(N-sec-butyl-N- ethylamino)-silacyclobutane

  1-(N-ethyl-N-cyclohexylamino)- silacyclobutane

  1-(N-ethyl-N-cyclopentylamino)- silacyclobutane

  1-(N-n-propyl-N-iso- propylamino)-silacyclobutane

  1-(N-sec-butyl-N-n- propylamino)- silacyclobutane

  1-(N-cyclohexyl-N-n- propylamino)-silacyclobutane

  1-(N-cyclopentyl-N-n- propylamino)-silacyclobutane

  1-(N,N-di-iso-propylamino)- silacyclobutane

  1-(N-sec-butyl-N-iso- propylamino)- silacyclobutane

  1-(N-cyclohexyl-N-iso- propylamino)-silacyclobutane

  1-(N-cyclopentyl-N-iso- propylamino)-silacyclobutane

  1-(N,N-di-sec-butylamino)- silacyclobutane

  1-(N-sec-butyl-N- cyclohexylamino)- silacyclobutane

  1-(N-sec-butyl-N- cyclopentylamino)- silacyclobutane

  1-(N-tert-butyl-N-iso- propylamino)-silacyclobutane

  1-(N-sec-butyl-N-tert- butylamino)-silacyclobutane

  1-(N-tert-butyl-N- cyclohexylamino)- silacyclobutane

  1-(N-tert-butyl-N- cyclopentylamino)- silacyclobutane

  1-(N,N-dicyclohexylamino)- silacyclobutane

  1-(N-cyclohexyl-N- cyclopentylamino)- silacyclobutane

  1-(N-phenyl-N-iso- propylamino)- silacyclobutane

  1-(N-sec-butyl-N- phenylamino)-silacyclobutane

  1-(N-cyclohexyl-N- phenylamino)-silacyclobutane

  1-(N-cyclopentyl-N- phenylamino)-silacyclobutane

  1-(N-ethyl-N-phenylamino)- silacyclobutane

  1-(N,N-dimethylamino)- silacyclobutane

  1-(N,N-diethylamino)- silacyclobutane

  1-(N,N-di-n-propylamino)- silacyclobutane

TABLE 14 Exemplary Organoaminocarbosilane (more specificallyorganoamino- 1,3-disilacyclobutane having cyclic four-membered ring)Compounds

  1-(N-methyl-N-iso- propylamino)-1,3- disilacyclobutane

  1-(N-sec-butyl-N- methylamino)-1,3- disilacyclobutane

  1-(N-cyclohexyl-N- methylamino)-1,3- disilacyclobutane

  1-(N-methyl-N- cyclopentylamino)-1,3- disilacyclobutane

  1-(N-ethyl-N-iso-propylamino)- 1,3-disilacyclobutane

  1-(N-sec-butyl-N- ethylamino)-1,3- disilacyclobutane

  1-(N-ethyl-N-cyclohexylamino)- 1,3-disilacyclobutane

  1-(N-ethyl-N-cyclopentylamino)- 1,3-disilacyclobutane

  1-(N-n-propyl-N-iso- propylamino)-1,3- disilacyclobutane

  1-(N-sec-butyl-N-n- propylamino)-1,3- disilacyclobutane

  1-(N-cyclohexyl-N-n- propylamino)-1,3- disilacyclobutane

  1-(N-cyclopentyl-N-n- propylamino)-1,3- disilacyclobutane

  1-(N,N-di-iso-propylamino)- 1,3-disilacyclobutane

  1-(N-sec-butyl-N-iso- propylamino)-1,3- disilacyclobutane

  1-(N-cyclohexyl-N-iso- propylamino)-1,3- disilacyclobutane

  1-(N-cyclopentyl-N-iso- propylamino)-1,3- disilacyclobutane

  1-(N,N-di-sec-butylamino)-1,3- disilacyclobutane

  1-(N-sec-butyl-N- cyclohexylamino)-1,3- disilacyclobutane

  1-(N-sec-butyl-N- cyclopentylamino)-1,3- disilacyclobutane

  1-(N-tert-butyl-N-iso- propylamino)-1,3- disilacyclobutane

  1-(N-sec-butyl-N-tert- butylamino)-1,3- disilacyclobutane

  1-(N-tert-butyl-N- cyclohexylamino)-1,3- disilacyclobutane

  1-(N-tert-butyl-N- cyclopentylamino)-1,3- disilacyclobutane

  1-(N,N-dicyclohexylamino)-1,3- disilacyclobutane

  1-(N-cyclohexyl-N- cyclopentylamino)-1,3- disilacyclobutane

  1-(N-phenyl-N-iso- propylamino)-1,3- disilacyclobutane

  1-(N-sec-butyl-N- phenylamino)-1,3- disilacyclobutane

  1-(N-cyclohexyl-N- phenylamino)-1,3- disilacyclobutane

  1-(N-cyclopentyl-N- phenylamino)-1,3- disilacyclobutane

  1-(N-ethyl-N-phenylamino)- 1,3-disilacyclobutane

  1-(N,N-dimethylamino)-1,3- disilacyclobutane

  1-(N,N-diethylamino)-1,3- disilacyclobutane

  1-(N,N-di-n-propylamino)-1,3- disilacyclobutane

TABLE 15 Exemplary Organoaminocarbosilane (more specifically 1,3-bis(organoamino)-1,3-disilacyclobutane having cyclic four-membered ring)Compounds

  1,3-bis(N-methyl-N-iso- propylamino)-1,3- disilacyclobutane

  1,3-bis(N-sec-butyl-N- methylamino)-1,3- disilacyclobutane

  1,3-bis(N-cyclohexyl-N- methylamino)-1,3- disilacyclobutane

  1,3-bis(N-methyl-N- cyclopentylamino)-1,3- disilacyclobutane

  1,3-bis(N-ethyl-N-iso- propylamino)-1,3- disilacyclobutane

  1,3-bis(N-sec-butyl-N- ethylamino)-1,3- disilacyclobutane

  1,3-bis(N-ethyl-N- cyclohexylamino)-1,3- disilacyclobutane

  1,3-bis(N-ethyl-N- cyclopentylamino)-1,3- disilacyclobutane

  1,3-bis(N-n-propyl-N-iso- propylamino)-1,3- disilacyclobutane

  1,3-bis(N-sec-butyl-N-n- propylamino)-1,3- disilacyclobutane

  1,3-bis(N-cyclohexyl-N-n- propylamino)-1,3- disilacyclobutane

  1,3-bis(N-cyclopentyl-N-n- propylamino)-1,3- disilacyclobutane

  1,3-bis(N,N-di-iso- propylamino)-1,3- disilacyclobutane

  1,3-bis(N-sec-butyl-N-iso- propylamino)-1,3- disilacyclobutane

  1,3-bis(N-cyclohexyl-N-iso- propylamino)-1,3- disilacyclobutane

  1,3-bis(N-cyclopentyl-N-iso- propylamino)-1,3- disilacyclobutane

  1,3-bis(N,N-di-sec- butylamino)-1,3- disilacyclobutane

  1,3-bis(N-sec-butyl-N- cyclohexylamino)-1,3- disilacyclobutane

  1,3-bis(N-sec-butyl-N- cyclopentylamino)-1,3- disilacyclobutane

  1,3-bis(N-tert-butyl-N-iso- propylamino)-1,3- disilacyclobutane

  1,3-bis(N-sec-butyl-N-tert- butylamino)-1,3- disilacyclobutane

  1,3-bis(N-tert-butyl-N- cyclohexylamino)-1,3- disilacyclobutane

  1,3-bis(N-tert-butyl-N- cyclopentylamino)-1,3- disilacyclobutane

  1,3-bis(N,N-dicyclohexylamino)- 1,3-disilacyclobutane

  1,3-bis(N-cyclohexyl-N- cyclopentylamino)-1,3- disilacyclobutane

  1,3-bis(N-phenyl-N-iso- propylamino)-1,3- disilacyclobutane

  1,3-bis(N-sec-butyl-N- phenylamino)-1,3- disilacyclobutane

  1,3-bis(N-cyclohexyl-N- phenylamino)-1,3- disilacyclobutane

  1,3-bis(N-cyclopentyl-N- phenylamino)-1,3- disilacyclobutane

  1,3-bis(N-ethyl-N- phenylamino)-1,3- disilacyclobutane

  1,3-bis(N,N-dimethylamino)- 1,3-disilacyclobutane

  1,3-bis(N,N-diethylamino)-1,3- disilacyclobutane

  1,3-bis(N,N-di-n-propylamino)- 1,3-disilacyclobutane

TABLE 16 Exemplary Organoaminocarbosilane (more specificallyorganoamino- methylsilane) Compounds

  N-methyl-N-iso-propylamino- methylsilane

  N-sec-butyl-N-methylamino- methylsilane

  N-cyclohexyl-N-methylamino- methylsilane

  N-methyl-N-cyclopentylamino- methylsilane

  N-ethyl-N-iso-propylamino- methylsilane

  N-sec-butyl-N-ethylamino- methylsilane

  N-ethyl-N-cyclohexylamino- methylsilane

  N-ethyl-N-cyclopentylamino- methylsilane

  N-n-propyl-N-iso-propylamino- methylsilane

  N-sec-butyl-N-n- propylamino-methylsilane

  N-cyclohexyl-N-n-propylamino- methylsilane

  N-cyclopentyl-N-n-propylamino- methylsilane

  N,N-di-iso-propylamino- methylsilane

  N-sec-butyl-N-iso- propylamino-methylsilane

  N-cyclohexyl-N-iso- propylamino-methylsilane

  N-cyclopentyl-N-iso- propylamino-methylsilane

  N,N-di-sec-butylamino- methylsilane

  N-sec-butyl-N- cyclohexylamino- methylsilane

  N-sec-butyl-N- cyclopentylamino-methylsilane

  N-tert-butyl-N-iso-propylamino- methylsilane

  N-sec-butyl-N-tert-butylamino- methylsilane

  N-tert-butyl-N- cyclohexylamino- methylsilane

  N-tert-butyl-N- cyclopentylamino-methylsilane

  N,N-dicyclohexylamino- methylsilane

  N-cyclohexyl-N- cyclopentylamino-methylsilane

  N-phenyl-N-iso-propylamino- methylsilane

  N-sec-butyl-N-phenylamino- methylsilane

  N-cyclohexyl-N-phenylamino- methylsilane

  N-cyclopentyl-N-phenylamino- methylsilane

  N-ethyl-N-phenylamino- methylsilane

  N,N-dimethylamino- methylsilane

  N,N-diethylamino-methylsilane

  N,N-di-n-propylamino- methylsilane

TABLE 17 Exemplary Organoaminocarbosilane (more specificallyorganoaminophenylsilane) Compounds

  N-methyl-N-iso-propylamino- phenylsilane

  N-sec-butyl-N-methylamino- phenylsilane

  N-cyclohexyl-N-methylamino- phenylsilane

  N-methyl-N-cyclopentylamino- phenylsilane

  N-ethyl-N-iso-propylamino- phenylsilane

  N-sec-butyl-N-n- propylamino-phenylsilane

  N-ethyl-N-cyclohexylamino- phenylsilane

  N-ethyl-N-cyclopentylamino- phenylsilane

  N-n-propyl-N-iso-propylamino- phenylsilane

  N-sec-butyl-N-n- propylamino-phenylsilane

  N-cyclohexyl-N-n-propylamino- phenylsilane

  N-cyclopentyl-N-n-propylamino- phenylsilane

  N,N-di-iso-propylamino- phenylsilane

  N-sec-butyl-N-iso- propylamino-phenylsilane

  N-cyclohexyl-N-iso- propylamino-phenylsilane

  N-cyclopentyl-N-iso- propylamino-phenylsilane

  N,N-di-sec-butylamino- phenylsilane

  N-sec-butyl-N- cyclohexylamino- phenylsilane

  N-sec-butyl-N- cyclopentylamino-phenylsilane

  N-tert-butyl-N-iso-propylamino- phenylsilane

  N-sec-butyl-N-tert-butylamino- phenylsilane

  N-tert-butyl-N- cyclohexylamino- phenylsilane

  N-tert-butyl-N- cyclopentylamino-phenylsilane

  N,N-dicyclohexylamino- phenylsilane

  N-cyclohexyl-N- cyclopentylamiro-phenylsilane

  N-phenyl-N-iso-propylamino- phenylsilane

  N-sec-butyl-N-phenylamino- phenylsilane

  N-cyclohexyl-N-phenylamino- phenylsilane

  N-cyclopentyl-N-phenylamino- phenylsilane

  N-ethyl-N-phenylamino- phenylsilane

  N,N-dimethylamino- phenylsilane

  N,N-diethylamino-phenylsilane

  N,N-di-n-propylamino- phenylsilane

In another embodiment of the method described herein, the compoundselected from orgnoaminosilane, organoaminodisilane, ororganoaminocarbosilane is reacted with a proton source to provide anorganoamine. In this embodiment, the step, of reacting the compound witha proton source, could be performed prior to or after the purificationof the compound. The reagents could be combined neat or, alternativelyin the presence of a solvent (e.g., at least one of the proton source orthe compound is dissolved in solvent). An excess of proton source can beused to drive the reaction to completion, aid in the purificationprocess, or both. Alternatively, a slight deficiency of the protonsource can be used to eliminate the need of separating unreacted protonsource from the organoamine product. In one particular embodiment, theproton source is delivered as a vapor into the reaction solutioncomprising the organoaminosilane. The protonation step (e.g., reactionof the proton source with the compound) could be performed in thetemperature range between −50° C. to 150° C. for the addition ofreagents and/or for the extent of the reaction. In some embodiments, theprotonation step may be carried out at lower temperature (below 0° C.)in order to help remove heat and prevent side reactions. In otherembodiments, higher temperatures (above 30° C.) may be preferred todrive the intended protonation reaction to completion. Reaction timescould range from 5 minutes to 30 minutes, to 1 h, to 6 h, to 12 h, to 24hr or more. The protonation reaction mixture may likely yield more thanone phase (liquid-liquid or liquid-solid) which can be separated byfiltration, decantation, separator funnel, distillation, adsorption,centrifugation, or other means. Purification of the end organoamineproduct may be accomplished by distillation, column chromatography, gaschromatography, sublimation, crystallization, or other purificationprocesses.

The following examples illustrate the method described herein forpreparing compounds such as, without limitation organoaminosilanes,organoaminodisilanes, organoaminocarbosilanes, and is not intended tolimit it in any way.

EXAMPLES

For the following examples, gas chromatography (GC-TCD), massspectrometry (GC-MS), and ¹H NMR spectroscopy were used to identify andquantify the solution compositions as appropriate. Gas chromatographicanalyses were carried out on the product effluent using a TCD equippedHP-5890 Series II GC and a 0.53 mm diameter×30 m Supleco columncontaining 3 μm thick SPB-5 media. Chloride analyses were performed byhydrolyzing the sample with water at 85° C. and injecting the liquidphase into a Metrohm Ion Chromatography instrument equipped with aconductivity detector.

Example 1 Synthesis of N,N-di-iso-propylaminosilane (cf. Table 2)

The catalyst Ru₃(CO)₁₂ (0.10 g, 0.16 mmol) was dissolved in the imineN-iso-propylidene-iso-propylamine (7.0 g, 71 mmol) and the resultingsolution was exposed to a silica source SiH₄ gas at 82 psia for 6 hoursat 40° C. The resulting reaction solution was determined by GC-MS tocontain N,N-di-iso-propylaminosilane. GC-MS showed the following peaks:131 (M+), 126 (M−15), 116, 110, 98, 88, 74.

Example 2 Synthesis of N,N-di-iso-propylaminodisilane (cf. Table 3)

The catalyst Ru₃(CO)₁₂ (0.10 g, 0.16 mmol) was dissolved in the imineN-iso-propylidene-sec-butylamine (7.0 g, 71 mmol) and the resultingsolution was exposed to a disilane Si₂H₆ gas at 102 psia for 6 hours at40° C. The reaction solution was determined by GC-MS to containN,N-di-iso-propylaminodisilane. GC-MS showed the following peaks: 161(M+), 146 (M−15), 128, 114, 104, 88, 72.

Example 3 Synthesis of 1-(N,N-di-iso-propylamino)-1,4-disilabutane (cf.Table 5)

A mixture of a silica source 1,4-disilabutane (0.48 g, 5.3 mmol) and theimine N-iso-propylidene-iso-propylamine (0.25 g, 2.5 mmol) was added toa stirred suspension of the catalyst, anhydrous NiCl₂ (0.02 g, 0.15mmol) in tetrahyrdofuran (THF) (1 mL), in a nitrogen-filled glovebox.After 2 days of stirring at room temperature, the resulting brownmixture was filtered to remove catalyst sediments and was determined byGC and GC-MS to contain the end product1-(N,N-di-iso-propylamino)-1,4-disilabutane. GC-MS showed the followingpeaks: 189 (M+), 188 (M−1), 174 (M−15), 159, 144, 130, 102.

Example 4 Synthesis of 1-(N,N-di-sec-butylamino)-1,4-disilabutane (cf.Table 5)

A mixture of a silica source 1,4-disilabutane (0.50 g, 5.54 mmol) andthe imine N-sec-butylidene-sec-butylamine (0.35 g, 2.75 mmol) was addedto a stirred solution of the catalyst (Ph₃P)₃RhCl (0.02 g, 0.02 mmol) inTHF (0.5 mL). After 1 day of stirring, the imine was completelyconsumed, and the resulting orange solution was determined by GC andGC-MS to contain the end product1-(N,N-di-sec-butylamino)-1,4-disilabutane. GC-MS showed the followingpeaks: 217 (M+), 202 (M−15), 189, 172, 158, 144, 132, 114, 102.

Example 5 Synthesis of1-(N-sec-butyl-N-iso-propylamino)-1,4-disilabutane (cf. Table 5)

A mixture of a silica source 1,4-disilabutane (0.50 g, 5.54 mmol) andthe imine N-sec-butylidene-iso-propylamine (0.32 g, 2.83 mmol) was addedto a stirred solution of the catalyst (Ph₃P)₃RhCl (0.02 g, 0.02 mmol) inTHF (0.5 mL). After 1 day of stirring, the imine was completelyconsumed, and the resulting orange solution was determined by GC andGC-MS to contain the end product1-(N-sec-butyl-N-iso-propylamino)-1,4-disilabutane. GC-MS showed thefollowing peaks: 203 (M+), 188 (M−15), 174, 158, 144, 130, 119, 102.

Example 6 Synthesis of1-(N,N-di-iso-propylamino)-1-methyl-silacyclopentane (cf. Table 12)

The solid catalyst Ca[N(SiMe₃)₂]₂ (0.01 g, 0.03 mmol) was added to amixture of a silica source 1-methyl-1-silacyclopentane (0.15 g, 1.5mmol) and the imine N-iso-propylidene-iso-propylamine (0.15 g, 1.5mmol). After 2 weeks, the pale yellow reaction solution was determinedby GC and GC-MS to contain1-(N,N-di-iso-propylamino)-1-methyl-1-silacyclopentane as the majorproduct. GC-MS showed the following peaks: 199 (M+), 179, 164, 148, 134,122, 107, 91, 81, 77.

Example 7 Synthesis of N,N-di-iso-propylamino-phenylsilane (cf. Table17)

A solution of the catalyst (Ph₃P)₃RhCl (0.01 g, 0.01 mmol) in THF (1 mL)was added to a stirred solution of a silica source phenylsilane (0.30 g,2.77 mmol) and the imine N-iso-propylidene-iso-propylamine (0.12 g, 1.21mmol). After 1 day of stirring, the imine was almost completelyconsumed, and the resulting orange solution was determined by GC andGC-MS to contain N,N-di-iso-propylamino-phenylsilane as the majorproduct. GC-MS showed the following corresponding peaks: 207 (M+), 192(M−15), 177, 164, 150, 134, 121, 107, 86, 72. Minor products observedinclude N,N-di-iso-propylaminosilane, bis(N,N-di-iso-propylamino)silane,and diphenylsilane.

Comparative Example 8 Synthesis of N,N-di-n-propylaminodiethylsilaneusing chlorosilane

Traditional method to make organoaminocarbosilane: Chlorodiethysilane(18.5 g, 151 mmol) was added dropwise to a stirred solution ofdi-n-propylamine (32.1 g, 317 mmol) in hexanes (250 mL) at −15° C. Theresulting white slurry was allowed to warm to room temperature whilestirring. The white solids were removed by filtration and the colorlessfiltrate was purified by vacuum distillation to obtain 22.2 g ofN,N-di-n-propylaminodiethylsilane. GC-MS showed the following peaks: 187(M+), 172 (M−15), 158, 144, 130, 116, 100, 87, 72. This product wasdetermined after hydrolysis to contain 537 ppm chloride.

Example 8 Synthesis of N,N-di-n-propylaminodiethylsilane

Claimed method to make organoaminocarbosilane: A solution of thecatalyst (Ph₃P)₃RhCl (0.40 mL, 0.029 M, 0.012 mmol) in THF was added toa stirred solution of a silica source diethylsilane (14.6 g, 165 mmol)and the imine N-n-propylidene-n-propylamine (14.4 g, 145 mmol). After 3days of stirring, the reaction solution was purified by vacuumdistillation to obtain 21.4 g of N,N-di-n-propylaminodiethylsilane. Thisproduct was determined after hydrolysis to contain 22 ppm chloride,demonstrating the hydrosilylation route provides much less chloridecontamination than the route employing chlorosilanes as startingmaterial. Furthermore, the chloride (or other halide) content can bereduced to non-detectable if halide-free catalysts are being employed inthe hydrosilylation.

Examples 9-21 Synthesis of Additional Organoaminosilane,Organoaminodisilane, or Organoaminocarbosilane Compounds

Additional organoaminosilanes, organoaminodisilanes, andorganoaminocarbosilanes were made via similar fashion as Examples 1 to 8and were characterized by GC-MS. The molecular weight (MW), thestructure, and corresponding major MS fragmentation peaks of eachcompound are provided in Table 18 to confirm their identification.

TABLE 18 Organoaminosilane, organoaminodisilane, ororganoaminocarbosilane compounds synthesized via hydrosilylation ofimines. MS Ex. Precursor Name MW Structure Peaks  9 N-sec-butyl-N-iso-propylamino silane (cf. Table 2) 145.32

145, 130, 116, 100, 88, 74 10 N,N-di-sec- butylaminosilane (cf. Table 2)159.35

159, 144, 130, 114, 100, 88, 74, 11 N-sec-butyl-N- iso-propylamino-disilane (cf. Table 3) 175.42

175, 160, 146, 128, 114, 104, 86, 72 12 N,N-di-sec- butylaminosilane(cf. Table 3) 189.45

189, 174, 160, 142, 128, 118, 104, 86, 72 13 1,2-bis(N,N-di-iso-propylamino) disilane (cf. Table 4) 260.57

260, 245, 229, 215, 187, 173, 158, 144, 128, 116, 100, 86 141,2-bis(N-sec- butyl-N-iso- propylamino) disilane (cf. Table 4) 288.63

288, 273, 259, 172, 158, 144, 130, 116, 100, 86, 72 15 1-(N-n-propyl-N-iso-propylamino)- 1,4-disilabutane (cf. Table 5) 189.45

189, 174, 160, 144, 130, 116, 102, 86 16 1,4-bis(N-n- propyl-N-iso-propylamino)- 1,4-disilabutane (cf. Table 6) 288.63

288, 274, 260, 244, 230, 216, 201, 188, 173, 160, 144, 128 171,4-bis(N,N-di- iso-propylamino)- 1,4-disilabutane (cf. Table 6) 288.63

288, 287, 243, 229, 207, 188, 144, 130 18 1,4-bis(N-sec- butyl-N-iso-propylamino)- 1,4-disilabutane (cf. Table 6) 316.68

316, 301, 281, 257, 243, 229, 215, 202, 186, 172, 158 19 1-(N,N-di-iso-propylamino)- silacyclopentane (cf. Table 11) 185.39

185, 170, 154, 142, 128, 112, 99, 85, 70 20 1-(N,N-di-iso- propylamino)-1,3-disilacyclo- butane (cf. Table 14) 187.43

187, 172, 159, 143, 130, 115, 101, 86, 73 21 1,3-bis(N,N-di- iso-propylamino)- 1,3-disila- cyclobutane (cf. Table 15) 286.61

286, 271, 243, 229, 213, 186, 172, 144, 128, 101, 87, 70

1. A method for preparing a compound selected from an organoaminosilane,an organoaminodisilane, and an organoaminocarbosilane, the methodcomprising the steps of: reacting an imine having a formula R—N═CR′R″wherein R, R′ and R″ are each independently selected from hydrogen, aC₁₋₁₀ linear alkyl group, a C₃₋₁₀ branched alkyl, a C₃₋₁₀ cyclic alkylgroup, a C₂₋₁₀ alkenyl group, a C₄₋₁₀ aromatic group, a C₄₋₁₀heterocyclic group, a C₁₋₁₀ linear organoamino group, a C₂₋₁₀ branchedorganoamino group, a silyl group, a C₁₋₁₀ linear carbosilyl group, and aC₂₋₁₀ branched carbosilyl group, wherein at least one of R′ and R″ or Rand R′, or none of R′ and R″ or R and R′ are be linked to form asubstituted or unsubstituted cyclic ring and a silicon source comprisinga hydridosilane in the presence of a catalyst under reaction conditionssufficient for the imine and silicon source to react and provide thecompound.
 2. The method of claim 1 wherein the compound comprises theorganoaminosilane and is at least one selected from the group consistingof: N,N-di-iso-propylaminosilane, N-sec-butyl-N-iso-propylaminosilane,N,N-di-sec-butyl-aminosilane, N-methyl-N-cyclopentylaminosilane,N-ethyl-N-cyclopentylaminosilane, N-cyclopentyl-N-n-propylaminosilane,N-cyclopentyl-N-iso-propylaminosilane, N-cyclohexyl-N-methylaminosilane,N-ethyl-N-cyclohexylaminosilane, andN-cyclohexyl-N-iso-propylaminosilane.
 3. The method of claim 1 whereinthe compound comprises the organoaminodisilane and is at least oneselected from the group consisting of: N,N-di-iso-propylaminodisilane,N-sec-butyl-N-iso-propylaminodisilane, N,N-di-sec-butyl-aminodisilane,N-ethyl-N-cyclopentylaminodisilane,N-cyclopentyl-N-n-propylaminodisilane,N-cyclopentyl-N-iso-propylaminodisilane,N-sec-butyl-N-cyclopentylaminodisilane,N-cyclohexyl-N-methylaminodisilane, N-ethyl-N-cyclohexylaminodisilane,and N-cyclohexyl-N-iso-propylaminodisilane.
 4. The method of claim 1wherein the compound comprises the organoaminocarbosilane and is atleast one selected from the group consisting of:1-(N,N-di-iso-propylamino)-1,4-disilabutane,1-(N,N-di-iso-propylamino)-1,3-disilapropane,1-(N,N-di-iso-propylamino)-2-methyl-1,3-disilapropane,1-(N,N-di-iso-propylamino)-1-silacyclopentane,1-(N,N-di-iso-propylamino)-1,3-disilacyclobutane,N,N-di-iso-propylamino-methylsilane,N-n-propyl-N-iso-propylamino-methylsilane,N-sec-butyl-N-iso-propylamino-methylsilane,N-cyclohexyl-N-iso-propylamino-methylsilane, andN,N-diethylamino-phenylsilane.
 5. The method of claim 1 wherein thecompound comprises 100 ppm or less of halide.
 6. The method of claim 5wherein the compound comprises 10 ppm or less of halide.
 7. The methodof claim 5 wherein the compound comprises 1 ppm or less of halide. 8.The method of claim 1 wherein the catalyst comprises a halide-freecatalyst and wherein the compound is substantially free of halide. 9.The method of claim 1 wherein the catalyst comprises an alkaline earthmetal complex.
 10. The method of claim 1 wherein the hydridosilane has aformula R¹R²R³SiH wherein R¹, R² and R³ are each independently selectedfrom hydrogen, a C₁₋₁₀ linear alkyl group, a C₃₋₁₀ branched alkyl group,a C₄₋₁₀ cyclic alkyl group, a C₂₋₁₀ alkenyl group, a C₄₋₁₀ aromaticgroup, a C₄₋₁₀ heterocyclic group, a C₁₋₁₀ linear organoamino group, aC₂₋₁₀ branched organoamino group, a silyl group, a C₁₋₁₀ linearcarbosilyl group, and a C₂₋₁₀ branched carbosilyl group and wherein atleast one of R¹ and R², R¹ and R³, R² and R³ or none of R¹ and R², R¹and R³, or R² and R³ are linked to form a substituted or unsubstitutedcyclic ring.
 11. A method of preparing an organoamine having a formulaHN(R)(CHR′R″) wherein R, R′ and R″ are each independently selected fromhydrogen, a C₁₋₁₀ linear alkyl group, a C₃₋₁₀ branched alkyl group, aC₃₋₁₀ cyclic alkyl group, a C₂₋₁₀ alkenyl group, a C₄₋₁₀ aromatic group,a C₄₋₁₀ heterocyclic group, a C₁₋₁₀ linear organoamino group, a C₂₋₁₀branched organoamino group, a C₁₋₁₀ linear carbosilyl group, and a C₂₋₁₀branched carbosilyl groups wherein at least one of R′ and R″ or R and R′or none of R′ and R″ or R and R′ are linked to form a substituted or anunsubstituted cyclic ring, the method comprising the steps of: reactingan imine having a formula R—N═CR′R″ wherein R, R′ and R″ are eachindependently selected from hydrogen, a C₁₋₁₀ linear alkyl group, aC₃₋₁₀ branched alkyl group, a C₃₋₁₀ cyclic alkyl group, a C₂₋₁₀ alkenylgroup, a C₄₋₁₀ aromatic group, a C₄₋₁₀ heterocyclic group, a C₁₋₁₀linear organoamino group, a C₂₋₁₀ branched organoamino groups, a silylgroup, a C₁₋₁₀ linear carbosilyl group, and a C₂₋₁₀ branched carbosilylgroup wherein at least one of R′ and R″ or R and R′ or none of R′ and R″or R and R′ are linked to form a substituted or unsubstituted cyclicring and a silicon source comprising a hydridosilane in the presence ofan alkaline earth metal catalyst under conditions sufficient for theimine and silicon source to react and provide a compound selected froman organoaminosilane, an organoaminodisilane, and anorganoaminocarbosilane; reacting the compound with a proton source underconditions sufficient to provide the organoamine.
 12. A method describedin claim 11 wherein the proton source is selected from the groupconsisting of water, alcohol, or Brønsted acid.
 13. Anorganoaminocarbosilane compound represented by the following structures:

wherein R, R′ and R″ are each independently selected from hydrogen, aC₁₋₁₀ linear alkyl group, a C₃₋₁₀ branched alkyl group, a C₃₋₁₀ cyclicalkyl group, a C₂₋₁₀ alkenyl group, a C₄₋₁₀ aromatic group, a C₄₋₁₀heterocyclic group, a C₁₋₁₀ linear organoamino group, a C₂₋₁₀ branchedorganoamino group, a silyl group, a C₁₋₁₀ linear carbosilyl group, and aC₂₋₁₀ branched carbosilyl group. and wherein at least one of R′ and R″or R and R′ or none of R′ and R″ or R and R′ are linked to formsubstituted or unsubstituted cyclic ring.